Process for production of vinyl chloride polymer

ABSTRACT

This process is a process for production of a vinyl chloride polymer by suspension polymerization or emulsion polymerization of vinyl chloride monomer or a mixture of vinyl chloride monomer with a vinyl monomer copolymerizable with said vinyl chloride monomer in an aqueous medium, characterized in that the polymerization is carried out in a polymerizer, the inner wall surface and portions of the auxiliary equipment thereof which may come into contact with the monomer during polymerization being previously coated with a scaling preventive comprising at least one selected from dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated π bonds, while controlling the chloride ion concentration in the reaction mixture to not higher than 100 ppm. According to said process, scaling onto the inner wall surface of a polymerizer, etc. during polymerization can be prevented effectively and surely.

This is a continuation of application Ser. No. 756,313, filed July 18,1985 and now abandoned.

This invention relates to a process for producing a vinyl chloridepolymer, particularly to improvement of scaling prevention on the innerwall surface of a polymerizer and so on in the course of polymerizationof vinyl chloride, etc.

In processes for suspension polymerization or emulsion polymerization ofvinyl chloride monomer or a mixture of vinyl chloride monomer and othervinyl monomers in the presence of a polymerization catalyst, there isinvolved the problem that polymer scales stick to the inner wall surfaceof the polymerizer or the portions of the auxiliary equipment of thepolymerizer which may come into contact with the monomer, such asstirrer, during polymerization. Scales sticking to the inner wall of thepolymerizer, etc. will result in a lower polymer yield and coolingcapacity of the polymerizer, and may also cause so called fish eyesformed by the adhering scales peeling off the inner wall of thepolymerizer and mixing in with the product, thereby lowering the qualityof the product. Further, the removal of the adhering scales requiresenormous amount of labor and time; in addition, unreacted monomers(vinyl chloride, etc.) are absorbed into the scales which may involvedisadvantageously the danger of bringing about hazards to the humanbody.

As the method for preventing scaling of polymer, it is known in the artto apply a coating of a chemical reagent (hereinafter referred to as"scaling preventive") on the inner wall surface of the polymerizer;various such scale preventives have been proposed. Among the variousknown methods, there is known a particularly good method in which a dyeand/or a pigment is used as the scaling preventive (Japanese PatentPublication No. 30835/1970). However, this method is not alwayseffective and sure in preventing scaling, and thus is not alwayssatisfactory.

Accordingly, an object of the present invention is to provide a processfor production of a vinyl chloride polymer which can surely preventscaling in the course of polymerization of vinyl chloride monomer or amixture of vinyl chloride monomer with other vinyl monomers.

The present inventors in attempting to improve on the method disclosedin Japanese Patent Publication No. 30835/1970 have consequently foundthat scaling can be prevented effectively and surely by use of a dye, apigment or a specific compound having at least 5 conjugated π bonds, andalso by controlling the chloride ions (Cl⁻) in the reaction mixtureduring polymerization.

According to the present invention, there is provided a process forproduction of a vinyl chloride polymer by suspension polymerization oremulsion polymerization of vinyl chloride monomer or a mixture of vinylchloride monomer with a vinyl monomer copolymerizable with said vinylchloride monomer in an aqueous medium, characterized in that thepolymerization is carried out in a polymerizer, the inner wall surfaceand portions of the auxiliary equipment thereof which may come intocontact with the monomer during polymerization being previously coatedwith a scaling preventive comprising at least one selected from dyes,pigments and aromatic or heterocyclic compounds having at least 5conjugated π bonds, while controlling the chloride ion concentration inthe reaction mixture to not higher than 100 ppm.

According to the process of the present invention, the scalingpreventing action possessed by the above scaling preventive can beinduced surely and potently, whereby scaling can effectively beprevented. Accordingly, no labor or time is required for scale removal,enabling continuous use of the polymerizer and improved runningefficiency. Also, the cooling capacity of the polymerizer can bemaintained constantly, without any fear of entrainment of the scalesinto the product, whereby the quality of the product polymer can beimproved.

Generally, the chloride ion concentration in the reaction mixture duringpolymerization of vinyl chloride monomer or a vinyl monomer mixturecontaining vinyl chloride monomer will increase abruptly at the initialstage of polymerization, thereafter tending to be increased slightly orremain at the same level until completion of polymerization. Theconcentration of the chloride ions may be considered to be influenced byvarious factors such as the contents of methyl chloride and hydrochloricacid contained in the vinyl monomer used as the starting material, thetemperature of the water used in charging, the degree of vacuum aftercharging, etc. The present inventors have found that the scalingpreventing action possessed by dyes, pigments and said compounds havingat least 5 conjugated π bonds can be surely induced by controlling saidchloride ion concentration in the reaction mixture throughout thepolymerization procedure to 100 ppm or less, and preferably to 50 ppm orless, to accomplish the present invention as mentioned above. If thechloride ion concentration in the reaction mixture during polymerizationexceeds 100 ppm, even if the aforesaid scaling preventive may be appliedon the inner wall surface of the polymerizer, etc., its effect as thescale preventive cannot fully be exhibited, whereby scaling cannoteffectively be prevented.

According to the present invention, one or more compounds selected fromdyes, pigments and aromatic or heterocyclic compounds having at least 5conjugated π bonds (hereinafter referred to simply as "conjugated π bondcompounds") may be used singly or in combination. However, it ispreferable to use a dye or pigment, and more preferably an azine dye.

The dyes and pigments which can be used as the scaling preventive in theprocess of the present invention may be exemplified by:

azo dyes such as monoazo and polyazo dyes and pigments, metal complexazo dyes and pigments, stilbene azo pigments, thiazole azo dyes and thelike;

anthraquinone dyes and pigments such as anthraquinone derivatives,anthrone derivatives and the like;

indigoid dyes and pigments such as indigo derivatives, thioindigoderivatives and the like;

phthalocyanine dyes and pigments;

carbonium dyes and pigments such as diphenylmethane dyes,triphenylmethane dyes and pigments, xanthene dyes, acridine dyes and thelike;

quinoneimine dyes such as azine dyes, oxazine dyes, thiazine dyes andthe like;

methine dyes such as polymethine or cyanine dyes and the like;

quinoline dyes;

nitro dyes;

benzoquinone and naphthoquinone dyes;

naphthalimide dyes and pigments;

perinone dyes;

sulfide dyes;

fluorescent dyes;

azoic dyes; and

reactive dyes.

These can be used either singly or in any desired combination of two ormore compounds. Of these dyes and pigments as exemplified above,particularly preferred are azine dyes, as mentioned above. Morespecifically, typical examples of these dyes and pigments are enumeratedbelow.

Azo dyes and pigments include the following compounds.

Exemplary monoazo and polyazo dyes are Basic Yellow 32, 34 and 36; BasicOrange 2, 32, 33 and 34; Basic Red 17, 18, 22, 23, 24, 32, 34, 38, 39and 40; Basic Violet 26 and 28; Basic Blue 58, 59, 64, 65, 66, 67 and68; Basic Brown 1, 4, 11 and 12; Basic Black 8; Azoic Diazo Component 4,21, 27 and 38; Disperse Yellow 3, 4, 5, 7, 8, 23, 50, 60, 64, 66, 71,72, 76, 78 and 79; Disperse Orange 1, 3, 5, 13, 20, 21, 30, 32, 41, 43,45, 46, 49, 50 and 51; Disperse Red 1, 5, 7, 12, 13, 17, 43, 52, 54, 56,58, 60, 72, 73, 74, 75, 76, 80, 82, 84, 88, 90, 97, 99, 101, 103, 113,117, 122, 125, 126, 128 and 129; Disperse Violet 10, 24, 33, 38, 41, 43and 96; Disperse Blue 85, 92, 94 and 106; Disperse Brown 3 and 5;Disperse Black 1, 2, 10, 26, 27, 28, 29, 30 and 31; Solvent Yellow 2, 6,14, 15, 16, 19, 21 and 56; Solvent Orange 1, 2, 5, 6, 14 and 45; SolventRed 1, 3, 23, 24, 25, 27 and 30; Solvent Brown 3, 5 and 20; SolventBlack 3; Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16,17, 23, 65, 73 and 83; Pigment Orange 1, 2, 5, 13, 14, 15, 16, 17, 24and 31; Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50,51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 112, 114 and 163; PigmentBlue 25; Pigment Green 10; Pigment Brown 1 and 2; Pigment Black 1;Direct Yellow 1, 8, 11, 12, 24, 26, 27, 28, 33, 44, 50, 58, 85, 86, 87,88, 89, 98, 100 and 110; Direct Orange 1, 6, 8, 10, 26, 29, 39, 41, 49,51, 57, 102 and 107; Direct Red 1, 2, 4, 13, 17, 20, 23, 24, 28, 31, 33,37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197,201, 218, 220, 224, 225, 226, 227, 228, 229, 230 and 231; Direct Violet1, 7, 9, 12, 22, 35, 51, 63, 90, 94 and 98; Direct Blue 1, 2, 6, 8, 15,22, 25, 71, 76, 77, 78, 80, 120, 123, 158, 160, 163, 165, 168, 192, 193,194, 195, 196, 203, 207, 225, 236, 237, 246, 248 and 249; Direct Green1, 6, 8, 28, 30, 31, 33, 37, 59, 63, 64 and 74; Direct Brown 1A, 2, 6,25, 27, 44, 58, 59, 101, 106, 173, 194, 195, 209, 210 and 211; DirectBlack 17, 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 94, 105, 106, 107,108, 112, 113, 117, 118, 132, 133 and 146; Acid Yellow 11, 17, 19, 23,25, 29, 36, 38, 40, 42, 44, 49, 61, 70, 72, 75, 76, 78, 79, 110, 127,131, 135, 141, 142, 164 and 165; Acid Orange 1, 7, 8, 10, 19, 20, 24,28, 33, 41, 43, 45, 51, 56, 63, 64, 65, 67 and 95; Acid Red 1, 6, 8, 9,13, 14, 18, 26, 27, 32, 35, 37, 42, 57, 75, 77, 85, 88, 89, 97, 106,111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145,154, 155, 158, 168, 249, 252, 254, 257, 262, 265, 266, 274, 276, 282,283 and 303; Acid Violet 7, 11, 97 and 106; Acid Blue 29, 60, 92, 113,117 and 120; Acid Green 19, 20 and 48; Acid Brown 2, 4, 13, 14, 20, 53,92, 100, 101, 236, 247, 266, 268, 276, 277, 282, 289, 301 and 302; AcidBlack 1, 7, 24, 26, 29, 31, 44, 76, 77, 94, 109 and 110; Mordant Yellow1, 3, 5, 23, 26, 30, 38 and 59; Mordant Orange 1, 4, 5, 6, 8, 29 and 37;Mordant Red 7, 9, 17, 19, 21, 26, 30, 63 and 89; Mordant Violet 5 and44; Mordant Blue 7, 13, 44, 75 and 76; Mordant Green 11, 15, 17 and 47;Mordant Brown 1, 14, 15, 19, 21, 33, 38, 40, 52 and 87; Mordant Black 1,3, 7, 9, 11, 17, 26, 32, 38, 43, 44, 51, 54, 65, 75, 77, 84, 85, 86 and87; Food Yellow 3 and 4; Food Red 7 and 9;

exemplary metal complex azo dyes are Solvent Yellow 61 and 80; SolventOrange 37, 40 and 44; Solvent Red 8, 21, 83, 84, 100, 109 and 121;Solvent Brown 37; Solvent Black 23; Acid Black 51, 52, 58, 60, 62, 63,64, 67, 72, 107, 108, 112, 115, 118, 119, 121, 122, 123, 131, 132, 139,140, 155, 156, 157, 158, 159 and 191; Acid Yellow 59, 98, 99, 111, 112,114, 116, 118, 119, 128, 161, 162 and 163; Acid Orange 74, 80, 82, 85,86, 87, 88, 122, 123 and 124; Acid Red 180, 183, 184, 186, 194, 198,199, 209, 211, 215, 216, 217, 219, 256, 317, 318, 320, 321 and 322; AcidViolet 75 and 78; Acid Blue 151, 154, 158, 161, 166, 167, 168, 170, 171,175, 184, 187, 192, 199, 229, 234 and 236; Acid Green 7, 12, 35, 43, 56,57, 60, 61, 65, 73, 75, 76, 78 and 79; Acid Brown 19, 28, 30, 31, 39,44, 45, 46, 48, 224, 225, 226, 231, 256, 257, 294, 295, 296, 297, 299and 300; Direct Yellow 39; Direct Violet 47 and 48; Direct Blue 90, 98,200, 201, 202 and 226; Direct Brown 95, 100, 112 and 170;

an exemplary stilbene azo dye is Direct Black 62 and

exemplary thiazole azo dyes are Direct Red 9 and 11.

Anthraquinone dyes and pigments include the following compounds.

Exemplary anthraquinone derivatives are Basic Violet 25; Basic Blue 21,22, 44, 45, 47, 54 and 60; Azoic Diazo Component 36; Vat Yellow 2, 3,10, 20, 22 and 33; Vat Orange 13 and 15; Vat Red 10, 13, 16, 31, 35 and52; Vat Violet 13 and 21; Vat Blue 4, 6, 8, 12, 14, 64, 66, 67 and 72;Vat Green 8, 13, 43, 44 and 45; Vat Brown 1, 3, 22, 25, 39, 41, 44, 46,57, 68, 72 and 73; Vat Black 8, 14, 20, 25, 27, 36, 56, 59 and 60;Disperse Orange 11; Disperse Red, 4, 9, 11, 15, 53, 55, 65, 91, 92, 100,104, 116 and 127; Disperse Violet 1, 4, 8, 23, 26, 28, 30 and 37;Disperse Blue 1, 3, 5, 6, 7, 20, 26, 27, 54, 55, 56, 60, 61, 62, 64, 72,73, 75, 79, 81, 87, 90, 91, 97, 98, 99, 103, 104 and 105; DisperseYellow 51; Solvent Violet 13 and 14; Solvent Blue 11, 12, 35 and 36;Solvent Green 3; Pigment Red 83 and 89; Pigment Blue 22; Acid Violet 31,34, 35, 41, 43, 47, 48, 51, 54, 66 and 68; Acid Blue 23, 25, 27, 40, 41,43, 45, 54, 62, 72, 78, 80, 82, 112, 126, 127, 129, 130, 131, 138, 140,142, 143, 182, 183, 203, 204 and 205; Acid Green 25, 27, 28, 36, 40, 41and 44; Acid Brown 27; Acid Black 48 and 50; Mordant Red 3 and 11;Mordant Blue 8 and 48; Mordant Black 13; Pigment Violet 5;

exemplary anthrone derivatives are Vat Yellow 1 and 4; Vat Orange 1, 2,3, 4 and 9; Vat Violet 1, 9 and 10; Vat Blue 18, 19 and 20; Vat Green 1,2, 3 and 9; Vat Black 9, 13, 29 and 57; Vat Red 13; Acid Red 80, 82 and83.

Indigoid dyes and pigments include the following compounds.

Exemplary indigo derivatives are Vat Blue 1, 3, 5, 35 and 41; ReducedVat Blue 1; Pigment Violet 19 and 122; Acid Blue 74 and 102; SolubilizedVat Blue 5 and 41; Solubilized Vat Black 1; Food Blue 1;

exemplary thioindigo derivatives are Vat Orange 5; Vat Red 1, 2 and 61;Vat Violet 2 and 3; Pigment Red 87 and 88; Vat Brown 3.

Phthalocyanine dyes and pigments may include, for example, Solvent Blue55; Pigment Blue 15, 16 and 17; Pigment Green 36, 37 and 38; Direct Blue86 and 199; Mordant Blue 58.

Carbonium dyes and pigments include the following compounds.

An exemplary diphenylmethane dye is Basic Yellow 2;

exemplary triphenylmethane dyes are Basic Red 9; Basic Violet 1, 3 and14; Basic Blue 1, 5, 7, 19, 26, 28, 29, 40 and 41; Basic Green 1 and 4;Solvent Violet 8; Solvent Blue 2 and 73; Pigment Violet 3; Pigment Blue1, 2 and 3; Pigment Green 1, 2 and 7; Direct Blue 41; Acid Violet 15 and49; Acid Blue 1, 7, 9, 15, 22, 83, 90, 93, 100, 103 and 104; Acid Green3, 9 and 16; Mordant Violet 1; Mordant Blue 1, 29 and 47; Food Violet 2;Food Blue 2; Food Green 2;

exemplary xanthene dyes are Basic Red 1; Solvent Red 49; Pigment Red 81and 90; Pigment Violet 1, 2 and 23; Acid Red 51, 52, 87, 92 and 94;Mordant Red 15 and 27; Food Red 14;

exemplary acridine dyes are Basic Orange 14 and 15.

Quinoimine dyes include the following compounds.

Exemplary azine dyes are Basic Red 2; Basic Black 2; Solvent Black 5 and7; Acid Blue 59; Acid Black 2;

exemplary oxiazine dyes are Basic Blue 3; Direct Blue 106 and 108;

exemplary thiazine dyes are Basic Yellow 1; Basic Blue 9, 24 and 25.

Methine dyes include the following compounds.

Exemplary polymethine (or cyanine) dyes are Basic Yellow 11, 13, 14, 19,21, 25, 28, 33 and 35; Basic Orange 21 and 22; Basic Red 12, 13, 14, 15,27, 29, 35, 36 and 37; Basic Violet 7, 15, 21 and 27.

Quinoline dyes may be exemplified by Basic Green 6; Disperse Yellow 54and 56; Solvent Yellow 33; Acid Yellow 3.

Nitro dyes may be exemplified by Disperse Yellow 1, 33, 39, 42, 49 and54; Acid Yellow 1.

Benzoquinone and naphthoquinone dyes may be exemplified by Disperse Blue58 and 108; Acid Brown 103, 104, 106, 160, 161, 165 and 188.

Naphthalimide dyes and pigments may be exemplified by Pigment Red 123;Vat Violet 23 and 39; Acid Yellow 7.

Perinone dyes may be exemplified by Vat Orange 7 and 15.

Sulfide dyes may include, for example, Solubilized Sulfur Yellow 2;Sulfur Yellow 4; Sulfur Orange 3, Sulfur Red 2, 3, 5 and 7; SolubilizedSulfur Blue 15; Sulfur Blue 2, 3, 4, 6, 7, 9 and 13; Sulfur Green 2, 3,6, 14 and 27; Solubilized Sulfur Brown 1 and 51; Sulfur Brown 7, 12, 15and 31; Sulfur Black 1, 2, 5, 6, 10, 11 and 15; Vat Yellow 35, 42 and43; Vat Blue 43 and 56.

Fluorescent dyes may include, for example, fluorescent brighteningagents 14, 22, 24, 30, 32, 37, 45, 52, 54, 55, 56, 84, 85, 86, 87, 90,91, 104, 112, 121, 134, 135, 153, 162, 163, 164, 166, 167, 168, 169,170, 171, 172, 173, 174, 175, 176 and 177.

Azoic dyes may include, for example, Azoic Diazo Component 17, 20, 22,24, 26, 31, 35, 41, 47, 48, 109 and 121; Azoic Coupling Component 2, 3,4, 5, 7, 8, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20, 23, 26, 28, 29, 35,36, 37, 41 and 108; Azoic Brown 2, 7, 11 and 15; Azoic Black 1 and 5;Azoic Yellow 1 and 2; Azoic Orange 2, 3 and 7; Azoic Red 1, 2, 6, 9, 16and 24; Azoic Violet 1, 2, 6, 7, 9 and 10; Azoic Green 1.

Reactive dyes may include, for example, Reactive Yellow 1, 2, 3, 4, 6,7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37 and 42;Reactive Orange 1, 2, 4, 5, 7, 13, 14, 15, 16, 18, 20, 23 and 24;Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21,22, 23, 24, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,45, 46, 49, 50, 58, 59, 63 and 64; Reactive Violet 1, 2, 4, 5, 8, 9 and10; Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20,21, 25, 26, 27, 28, 29, 31, 32, 33, 34, 37, 38, 39, 40, 41, 43, 44 and46; Reactive Green 5, 6, 7 and 8; Reactive Brown 1, 2, 5, 7, 8, 9, 10,11, 14 and 16; Reactive Black 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14 and18.

Further, pigments may be exemplified by inorganic pigments such asChrome Yellow, Zinc Yellow, ZTO type zinc chromate, red lead, iron oxidepowder, zinc white, aluminum powder and zinc powder.

The "conjugated π bond" possessed by the conjugated π bond compoundwhich may be used as the scaling preventive in the process of thepresent invention herein means two or more double bonds and/or triplebonds in conjugated relationship. And, the aromatic compounds having atleast 5 conjugated π bonds which may be used in the present inventionmay include benzene derivatives, naphthalene derivatives, polynucleararomatic compounds, quinones, non-benzene type aromatic compounds, etc.,having at least five conjugated π bonds. On the other hand, theheterocyclic compounds having at least 5π bonds may include, forexample, oxygen-containing heterocyclic compounds, nitrogen-containingheterocyclic compounds, sulfur-containing heterocyclic compounds,bicyclic compounds having a nitrogen atom in common, alkaroids, etc.,having at least 5 conjugated π bonds. Specific examples of thesecompounds are enumerated below.

The aromatic compounds having at least 5 bonds include the followingcompounds.

First, as benzene derivatives, there may be included:

phenols and derivatives thereof, such as 2,6-ditert-butylphenylphenol,catecholphthalein, 2,2-diphenylolpropane, 3,7-dioxy-10-methylxanthene,phenolphthalein, 7-oxy-2,4-dimethylbenzopyrooxonium chloride,oxyanthraquinone, purpurogallin, Gallein, diphenylether,α-methoxyphenazine, chloroglucide, 2,3-dioxyanthraquinone,5,7-dioxy-4-methylcoumarine, dioxyacridone, salicylic acid,α-hydrindone, β-phenylbutyrophenyl,N-2,4-dinitrophenyl-N-phenylhydroxylamine,1-(4-nitrophenyl)-3,5-dimethylpyrazole, 9,10-diphenylphenanthrene,acetophenone;

aromatic amines and derivatives thereof, such asN-phenyl-p-benzoquinonediamine, quinoline, Safranine B, Rosaniline,Indiurine Spirit Soluble, Aniline Black, Para-Rosaniline, Methyl Violet,Methyl Orange, Methyl Red, Indigo, carbazole, Methylene Blue,o-phenanthroline, p-phenanthroline, 3,6-diaminoacridine, IndanthreneScarlet 2G, 4-aminodiphenylamine, Acridine Yellow, 3-aminophenothiazine,N'-diphenyl-p-phenylenediamine, Rhodamine, 7-amino-4-methylcoumarine,2-aminophenazine, phenothiazine, diphenylamine, N-methylphenylamine,N-phenyltolylamine, ditolylamine, 2-oxy-4-methylquinoline, Hansa YellowG, N,N'-diphenylformamidine, phenanthrophenazine, Bismarck Brown G,2,3-diaminophenazine, 2-aminodiphenylamine, Chrysodine R,2,3,7,8-tetraaminophenazine, aminophenoxazone, oxyphenoxazone,Triphenylenedioxazine, 2,4-dinitrophenoxazine,2',4'-dinitro-4-oxy-3-aminophenylamine;

nitro and nitroso derivatives, such as p-nitrosodiphenylhydroxylamine,phenazine, phenazine oxide, 1-phenylazo-2-naphthol, 4-nitroxanthone,4'-nitroso-2-nitrodiphenylamine;

phenylhydroxylamine derivatives, such as 4,4'-dinitrodiphenylamine,oxalic acid bis(β-phenylhydrazine), malonic acid bis(β-phenylhydrazine),succinic acid bis(β-phenylhydrazine), phthalic acidbis(β-phenylhydrazine);

aromatic halides, such as biphenyl chloride;

aromatic aldehydes, such as 2-phenyl-1-benzyl-benzimidazole,Leucomalachite Green, Malachite Green, tetrachlorohydroquinonemonobenzoate, benzoflavin, 2-phenylbenzthiazole,4-benzhydrylbenzaldehyde, bisphenylhydrazone,bis(4-nitrophenylhydrazone);

aromatic ketones such as triphenylisooxazole, benzophenone potassium,4-methylbenzophenone, p-toluyl acid anilide, benzoic acid toluidide,duryl phenyl ketone, 2,4,2',4'-tetramethylbenzophenone,calchonphenylhydrazone, 1,3,5-triphenylpyrazoline, dinitrobenzyl;

benzoic acids, phthalic acids and derivatives thereof, such asquinizaline, nitrodiphenylether;

benzene derivatives having further one substituent other than aldehydegroup, such as disalicylaldehyde, coumarine, 2-benzoylcoumarone,1-oxy-2,4-dimethylfluorone, 3-phenylcoumarone, ethylcoumarine-3-carboxylate, 3-acetylcoumarine, hydrovaniloin,4-oxy-3-methoxy-ω-nitrostyrene, α-(nitrophenyl)-β-benzoylethyleneoxide,dinitrophenylindazole, 5-chloro-3-(4-oxyphenyl)anthramil,3-nitroacridone, 6-nitro-3-phenylanthramil,2,8-dimethyl-1,9-anthrazoline, carboxtyrin, 1,3-dioxyacridine,oxyquinacdine, Phlorchinyl, 2-methylquinazoline,3-acetyl-2-methylquinoline, 2-oxy-3-phenylquinoline, 3-nitroquinoline,quinoline-2,3-dicarboxylic acid ester;

benzene derivatives having further one substituent other than acylgroup, such as 7-oxyflavanone, 7-oxyflavone, 7,8-dioxyflavone,7-acetoxy-4-methyl-3-phenylcoumarine,7,8-diacetoxy-4-methyl-3-phenylcoumarine, o-oxybenzophenone, xanthone,2-phenylbenzooxazole, m-oxybenzophenone, p-oxybenzophenone,2-benzoylxanthone, 2,4-dioxybenzophenone, 2,5-dioxybenzophenone,2,2'-dioxybenzophenone, xanthene, aurin, trioxybenzophenone,6,7-dimethoxy-3-phenylcoumarone, 0-nitrobenzophenone,m-nitrobenzophenone, 4,4'-dibenzoylazoxybenzene,2-(2-aminophenyl)-4-methylquinone, 2-oxy-4-methylquinone, acridone,2,4-dimethylquinazoline, 3-cyan-2-oxy-4-methylquinoline, fluorene,anhydro(2-aminobenzophenone) dimer, 2-oxy-3-phenylindazole,3-phenylindazole, 2-phenylbenzimidazole, 2-methyl-8-benzoylquinoline,2-methyl-4-phenylquinoline, 4-phenyl-2-quinazolone, aminobenzophenone,chlorobenzophenone, 4-phenylbenzo-1,2,3-triazine-3-oxide,diaminobenzophenone, 7-methyl-3-phenyl-4,5-benzo-1,2,6-oxydiazine,4,4'-bisdimethylaminobenzophenone,4,4'-bisdimethylaminobenzophenonemide, 2,4-dinitro-9-phenylacridine,4,4'-dibenzoyldiphenyl;

benzene, toluene derivatives having three or more differentsubstituents, such as tetramethoxyindigo,5,6,5',6'-bismethylenedioxyindigo,7-acetoxy-8-methoxy-3-(2-nitrophenyl)carbostyryl,2,2'-dinitrodiphenyldisulfide-4,4'-dialdehyde,6-chloro-3-benzoylflavone, 1,3,8-trinitrophenoxazine;

aralkyl compounds, such as 9-benzylacridine;

diazo compounds and azo compounds, such as azobenzene, azotoluene,2,2-dimethoxyazobenzene, 4,4'-dichloroazobenzene, 1,1'-azonaphthalene,2,2'-dioxyazobenzene, 2,2'-dioxy-5,5'-dimethylazobenzene,p-bromoazobenzene, p-nitroazobenzene, phenoazoxide;

aromatic unsaturated compounds, such as2,3,4,5-tetraphenylcyclopentane-2-ene-1-one, 1,2,3-triphenyleneazulene,2,2'-dimethyldiphenylacetylene, 4,4'-diethyldiphenylacetylene,3,4,3',4'-tetramethyldiphenylacetylene, 2,2'-dichlorodiphenylacetylene,2,2'-dibromodiphenylacetylene, 2-nitrodiphenylacetylene,2,2'-dinitrodiphenylacetylene, 2,2'-diaminodiphenylacetylene,2,2'-dimethoxy-diphenylacetylene, stilbene, α-methylstilbene,α-ethylstilbene, α,β-dimethylstilbene, α,β-diethylstilbene,α,β-dichlorostilbene, α,β-dibromostilbene, 2-chlorostilbene,4,4'-diiodostilbene, α-nitrostilbene, α,β-dinitrostilbene,2,4,6-trinitrostilbene, 2-aminostilbene, 2,2'-diaminostilbene,4,4'-di(dimethylamino)stilbene, 2,2'-dicyanstilbene, 2-oxystilbene,2-methoxystilbene, 2,2'-dioxystilbene, 2,2'-dimethoxystilbene,4,4'-dialkoxystilbene, 3,5,2',4'-tetraoxystilbene; and

polyphenyls and derivatives thereof, such as biphenyl, terphenyl,quaterphenyl, quinophenyl, sexiphenyl, septiphenyl, octiphenyl,noviphenyl, deciphenyl, etc.

Next, as naphthalene derivatives, there may be included:

alkyl, alkenyl and phenylnaphthalenes, such as 1-methylnaphthalene,2-methylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene,1,2-dimethylnaphthalene, 1,4-dimethylnaphthalene,1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene,1,7-dimethylnaphthalene, 2,3-dimethylnaphthalene,2,6-dimethylnaphthalene, 2,7-dimethylnaphthalene, 1-propylnaphthalene,1-isopropylnaphthalene, 2-isopropylnaphthalene, trimethylnaphthalene,diisopropylnaphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene,1-propenylnaphthalene, 1-allylnaphthalene, 1-isopropenylnaphthalene,2-isopropenylnaphthalene, 1-phenylnaphthalene, 2-phenylnaphthalene,1,4-diphenylnaphthalene, 1,2,4-triphenylnaphthalene;

dinaphthyls, such as 1,1'-dinaphthyl, 1,2'-dinaphthyl, 2,2'-dinaphthyl;

naphthylarylmethanes, such as 1-benzylnaphthalene, 2-benzylnaphthalene,1-(α-chlorobenzyl)naphthalene, 1-(α,α-dichlorobenzyl)naphthalene,diphenyl-α-naphthylmethane, diphenyl-β-naphthylmethane,1,8-dibenzylnaphthalene, di-α-naphthylmethane,α-naphthyl-β-naphthylmethane, di-β-naphthylmethane;

naphthylarylethanes, such as 1-phenethylnaphthalene,1,2-di-α-naphthylethane, 1,2-di-β-naphthylethane,1,1-α-dinaphthylethane;

hydronaphthalenes such as 1,2-dihydronaphthalenes,1,4-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalene;

nitronaphthalenes and derivatives thereof, such as dinaphthylpyridazine,7,8-benzoquinone, 5,6-benzoquinone, naphthazarine, diperimidine,nitromethylnaphthalene, nitromethylnaphthalene, nitrophenylnaphthalene,halo-nitronaphthalene, halo-dinitronaphthalene, nitrosonaphthalene,dinitrotetraline, dibenzophenazine, methylbenzoindole,9-chloro-1-azaanthracene, quinolinoquinoline, 1,2,3-triazaphenarene,perimidone, perimidine, dibenzoacridine, benzophenazine-12-oxide,diaminonaphthalene, triaminonaphthalene, tetraaminonaphthalene,N-ethyl-α-naphthylamine, N-methylnaphthylamine,N,N-dimethylnaphthylamine, N-methyl-N-ethylnaphthylamine,N-methyl-N-ethylnaphthylamine, trimethylnaphthyl ammonium salt,N-phenylnaphthylamine, N-benzylnaphthylamine, N-naphthylethylenediamine,N-naphthylglycine, N-β-cyanomethylnaphthylamine, N-acetylnaphthylamine,N-formylnaphthylamine, N-benzoylnaphthylamine, N-phthaloylnaphthylamine,aminomethylnaphthalene, nitronaphthylamine, dinitronaphthylamine,halo-nitronaphthylamine, aminotetraline, diaminotetraline;

halogenated naphthalenes, such as 1-fluoronaphthalene,1-chloronaphthalene, 1-chloro-3,4-dihydronaphthalene, 1-iodonaphthalene,1-bromonaphthalene, 1-chloro-4-chloromethylnaphthalene,1-bromo-2-(bromomethyl)naphthalene, 1,4-difluoronaphthalene,1,2-dichloronaphthalene, 1,6-dichloronaphthalene,1,7-dichloronaphthalene, 1,5-dichloronaphthalene,1,8-dichloronaphthalene, 2,3-dichloronaphthalene,1,4-dibromonaphthalene, 1,4-diiodonaphthalene, perylene,1,2,3-trichloronaphthalene, 1,2,4-tribromonaphthalene,1,2,3,4-tetrachloronaphthalene, 1,4,5-tribromo-3,8-dimethylnaphthalene,1,3,6,7-tetrachloronaphthalene, 1,3,5,8-tetrabromonaphthalene,1,2,3,4,5-pentachloronaphthalene;

naphthylhydroxylamines, naphthylpyrazines and naphthylureas, such asα-naphthylhydroxylamine, N'-phenyl-N-α-naphthyl-N-oxyurea,β-naphthylthiohydroxylamine, N-nitroso-α-naphthylhydroxylamine,Neocupferron, 2-oxy-1,1'-azonaphthalene, α-naphthylhydrazine,1,2-dibenzocarbazole, 4,4-diamino-1,1'-binaphthyl, 3,4-benzocarbazole,2,2'-diamino-1,1'-binaphthyl, N'-acetyl-N-β-naphthylhydrazine,N'-lauroyl-N-β-naphthylhydrazine, N'-phenyl-N-α-naphthylhydrazine,N'-(2,4-dinitrophenyl)-N-α-naphthylhydrazine,2-α-naphthyl-5-nitrobenztriazole, N,N'-di-α-naphthyldrazine,1,1'-diamino-2,2'-binaphthyl, N,N'-di-5-tetralylhydrazine,N'-(2,4-dinitrophenyl)-N-β-naphthylhydrazine,2-β-naphthyl-5-nitrobenztriazole,N'-triphenylmethyl-N-β-naphthylhydrazine, N,N'-di-β-naphthylhydrazine,N-methyl-N-(2,4-dinitro-1-naphthyl)hydrazine,2-amino(naphtho-1',2'-:4,5-thiazole), 1,2:5,6-dibenzophenazine,2-amino-(naphtho-2',1':4,5-thiazole), 2,3-dihydrazinonaphthalene,2-phenyl-1,3-bisbenzylideneamino(naphtho-2',3':4,5-imidazoline),N-acetyl-α-naphthylnitrosoamine, N-ethyl-α-naphtylnitrosoamine,N-phenyl-α-naphthylnitrosoamine, α,α'-dinaphthylnitrosoamine, succinicacid bis(β-naphthylnitrosoamide), N-ethyl-β-naphthylnitrosoamine,N-phenyl-β-naphthylnitrosoamine,N-acetyl-2-methyl-1-naphthylnitrosoamine, 4,5-benzindazole,naphthylnitrosoamine, 1-nitro-2-naphthylamine, α-naphthylurea,N,N'-di-α-naphthylurea, 4-chloro-1-naphthylcarbamoylchloride,2,4'-dichloro[naphtho-1',2':4,5-thiazole],2-mercapto[naphtho-1',2'-:4,5-thiazole],2-chloro[naphtho-1',2':4,5-thiazole],2-mercapto[naphtho-2',1':4,5-thiazole],2-chloro[naphtho-2',1':4,5-thiazole];

naphthalene type aralkyl compounds, such as dibenzoanthracene,acenaphthene, α-chloroethylnaphthalene, phenylnaphthylchloromethane,diphenylnaphthylchloromethane, nitromethylnaphthalene,aminomethylnaphthalene, (naphthylemethyl)amine,α-phenyl(naphthylmethyl)amine, N-benzyl(naphthylmethyl)amine,trimethyl(naphthylmethyl)ammonium salt, tri(naphthylmethyl)amine,di(naphthylmethyl)amine, (β-naphthylethyl)alcohol,dimethylnaphthylcarbinol, phenylnaphthylcarbinol,diphenylnaphthylcarbinol, 9-phenylbenzofluorene, naphthylpropyleneoxide,ethyl(naphthylmethyl)ether, phenyl(naphthylmethyl)ether,naphthylacetaldehyde, naphthylacetone, ω-naphthylacetophenone,acenaphthenone, dihydrophenarone, phenarone, benzoindanone,naphthylacetonitrile, 9,9'-dichlorodibenzofluorene,α-nitro-β-naphthylethylene, γ-naphthylallyl alcohol, β-naphthylacrolein,methyl(β-naphthylvinyl)ketone, naphthylphenanthrene dicarboxylic acidanhydride;

naphthol, naphthalenesulfonic acids, such as 9-oxynaphtacenequinone,2'-naphthalene-2-indoleindigo, 1-methoxynaphthalene,1-ethoxynaphthalene, 1-phenoxynaphthalene, α-naphtholsalicylic acidester, β-naphthol, α-naphthol, α-naphtholbenzoic acid ester,α-naphtholacetic acid ester, phenyl-β-oxynaphthylbenzaliminomethane,β-naphtholphenylmethylamine, methylene-di-β-naphthol, dinaphthopyrane,1'-naphthol-2-indoleindigo, 2-methoxynaphthalene, 2-ethoxynaphthalene,N-p-oxyphenyl-2-naphthylamine base, β-naphtholsalicylic acid ester,2-methyl-1-naphthol, 1,2-naphthamethylenequinone, 1,2-dioxynaphthalene,naphthaleneindoleindigo, α,β-naphthophenoxazine, β,γ-naphthophenoxazine,4-oxy-10-methyl-1',2'-benzocarbazole, dioxynaphthfluorane,dinaphthoquinone, 2,6-naphthoquinone, oxybenzoacridine,9-oxy-3-dimethylaminonaphthophenoxazine, 1,2,4-trioxynaphthalene,1,4,5,6-tetraoxynaphthalene, thio-α-naphthol, 4-mercapto-1-naphthol,1,5-naphthalenedithiol, methyl-α-naphthyl sulfide, 1,1'-naphthylsulfide, 1,1'-thiodi-2-naphthol, 1,1'-naphthyl disulfide1,1'-thiodi-1-naphthol, thio-β-naphthol, naphthothioindigo,1-amino-2-naphthalenethiol, naphthothianthrene,2-mercapto-1,2-naphthothiazole;

naphthoaldehydes and derivatives thereof, such as α-naphthoaldehyde,2-(2,4-dinitrophenyl)-1-(α-naphthyl)ethylene,2-methyl-1-naphthoaldehyde, 2,3-dimethyl-1-naphthoaldehyde,4-bromo-1-naphthoaldehyde, 4-nitro-1-naphthoaldehydes,2,4-dinitro-1-naphthoaldehyde, 4-amino-1-naphthoaldehyde,2-oxy-1-naphthoaldehyde, 1-naphthalene-2'-indoleindigo,1,2-bis(2-oxy-1-naphthyl)ethylene, 1,2:7,8-dibenzoxanthilium chloride,2-oxy-1-naphthylethenyl pyrylium salt, 5,6-benzocoumarin,bis(2-methyl-3-indolyl)(2-oxy-1-naphthyl)methane, 4,5-benzindoxazene,2-acetoxy-1-naphthonitrile, 4-methoxy-1-naphthoaldehyde,1,4-bis(4-methoxy-1-naphthyl)-1,3-butadiene,2-naphthalene-2'-indoleindigo, 3-acetyl-6,7-benzocoumarin,4-chloro-1-oxy-2-naphthoaldehyde, naphthalenedialdehyde,5-oxy-2-naphthaleneindoleindigo, 5,6,7,8-tetrahydro-2-naphthoaldehyde,imide chloride, naphthoamide, naphthoanilide, naphthonitrile, ethylβ-naphthoimidate, β-naphthamidine, α-naphthoamidoxime,α-naphthohydrazide, naphthostyryl, oxynaphthonitrile,1,2:7,8-dibenzoxanthone, 1,2-benzoxanthone,1,1'-binaphthylene-2,8';8,2'-dioxide, 2,3;6,7-dibenzoxanthone,3-oxy-2-naphthoanilide, 1,3-bis(3-oxy-2-naphthoyloxy)benzene,2,4-dioxyphenyl-3-oxy-2-naphthyl ketone,4-arylazo-3-oxy-2-naphthoanilide,3,4-dihydronaphthalene-1,2-dicarboxylic acid anhydride,2-aminonaphthalimide, naphthalohydrazide, α-pyridonaphthalone,N-methylnaphthalimide; and

acetonaphthenes, benzoylnaphthenes, such as 1,2:5,6-dibenzanthracene,2'-methyl-2,1'-dinaphthyl ketone, 2-methyl-1,1'-dinaphthyl ketone,styryl-2-naphthyl ketone, β-naphthoyl acetone, β-naphthoylacetophenone,1-(β-naphthyl)-1-chloroethylene,2-[tris(β-cyanoethyl)acetyl]naphthalene, 1,3,5-tris(β-naphthyl)benzene,dimethyl-2-naphthylcarbinol, 4,5:4',5'-dibenzothioindigo,styryl-1-naphthyl ketone, β-acetonaphthone, 1-propionylnaphthalene,1-butylnaphthalene, 1-isobutylnaphthalene, 1-stearoylnaphthalene,1-benzoylnaphthalene, 1-o-toluylnaphthalene, p-biphenyl-1-naphthylketone, 1,2,5,6-dibenzanthracene, 1-acetyl-3,4-dihydronaphthalene,1-acetyl-7-bromonaphthalene, 1-aminoacetylnaphthalene,2-aminobenzoylnaphthalene, 1-acetyl-2-oxynaphthalene,1-acetyl-2-methoxynaphthalene, 1-acetyl-4-ethoxynaphthalene,2-cinnamoyl-1-naphthol, 7,8-benzochromone,3-acetyl-2-methyl-7,8-benzochromone, 3,4-dimethyl-7,8-benzocoumarin,4-methyl-3-phenyl-7,8-benzocoumarin, 1-benzoyl-2-oxynaphthalene,4-oxybenzanthrone, 4-benzoyl-1-naphthol, 3-oxy-1,2-benzofluorenone,2-acetyl-4-chloro-1-oxynaphthalene, α-naphthylglyoxal,β-naphthylglyoxal, 1,4-dibenzoylnaphthalene,phenyl-4-methyl-1-naphthyldiketone, and the like.

Also, as the polynuclear aromatic compounds, there may be included:

anthracenes and derivatives thereof, such as anthracene,1,2-dihydoanthracene, 1-chloroanthracene, 1,4-dichloroanthracene,1,2,7-trichloranthracene, 1,2,3,4-tetrachloroanthracene,1-nitroanthracene, 9,10-dinitroanthracene, 1-aminoanthracene,2-dimethylaminoanthracene, 2-anilinoanthracene, 9-methylaminoanthracene,1,4-diaminoanthracene, 1-oxyanthracene, 9,10-dihydroanthrol,10-methylanthranol, 10-phenylanthranol, 10-nitroanthranol,2-amino-1-anthranol, 1,2-dioxyanthracene, 9,10-dioxyanthracenediacetate, 1-methylanthracene, 4-chloro-1-methylanthracene,1,5-dichloro-2-methylanthracene, 9-ethylanthracene, 9-vinylanthracene,9-propylanthracene, 9-isopropylanthracene, 9-butylanthracene,9-isobutylanthracene, 9-isoamylanthracene, 1,3-dimethylanthracene,9,10-diethylanthracene, 1-phenylanthracene, 9-phenylanthracene,1,5-dichloro-9-phenylanthracene, 10-nitro-9-phenylanthracene,9-benzylanthracene, 1-benzhydrylanthracene, 9,10-diphenylanthracene,9,10-dibenzylanthracene, 9,10-diphenyl-9,10-dihydroanthracene,1-(β-naphthyl)anthracene, 9-(α-naphthyl)-10-phenylanthracene,9,10-di(α-naphthyl)anthracene, 1,1'-bianthryl, 2,2'-bianthryl,9,9'-bianthryl, anthracene-9-aldehyde, 1-acetylanthracene,9-benzoylanthracene, 10-nitroanthraphenone, 9,10-dibenzoylanthracene,anthrone, 9-mercaptoanthracene, 9,10-disodium-9,10-dihydroanthracene,10-bromo-9-anthrylmagnesium bromide, Anthryl-mercury chloride;

phenanthrenes and derivatives thereof, such as phenanthrene,9,10-dihydrophenanthrene, 1,2,3,4-tetrahydrophenanthrene,1-chlorophenanthrene, phenanthrene-9,10-dichloride, 1-bromophenanthrene,1-iodophenanthrene, 9-(chloromethyl)phenanthrene,1-(bromomethyl)phenanthrene, 4,5-bis(bromomethyl)phenanthrene,1-nitrophenanthrene, 10-bromo-9-nitrophenanthrene, 1-aminophenanthrene,9,10-diaminophenanthrene, 9,9'-azoxyphenanthrene, 9,9'-azophenanthrene,1-oxyphenanthrene, cholesterol, estrone, androsterone,10-bromo-9-phenanthrol, 9-nitro-3-phenanthrol, 4-amino-1-phenanthrol,10-benzoazo-9-phenanthrol, 1,2-dioxyphenanthrene, retene-3,8-diol,2,3,5,6-tetraoxyphenanthrene, 1-methylphenanthrene, 1-ethylphenanthrene,1-vinylphenanthrene, 1,2-dimethylphenanthrene, 9,10-diethylphenanthrene,9,10-dipropylphenanthrene, 2-ethyl-1-methylphenanthrene,7-isopropyl-1-methylphenanthrene, 9,10-dihydroretene, aminoretene,3-acetoaminoretene, 6-acylaminoretene, 9-phenylphenanthrene,9-benzylphenanthrene, 1-(α-naphthyl)phenanthrene, 1,1'-biphenanthryl,9,9'-biphenanthryl, 1-phenanthraldehyde, 2-phenanthraldehyde,9-phenanthraldehyde, 1-acetylphenanthrene, 2-propionylphenanthrene,3-acetylretene, 1-benzoylphenanthrene;

phenanthrenequinones, such as phenanthrene-1,2-quinone,phenanthrene-1,4-quinone, phenanthrene-3,4-quinone,phenanthrene-9,10-quinone, 2-phenyl-3-acetoxy-4,5-biphenylfuran,7-isopropyl-1-methylphenanthrenequinone, 1-chlorophenanthrenequinone,2-bromophenanthrenequinone, 2-iodophenanthrenequinone,2,7-dibromophenanthrenequinone, 2-nitrophenanthrenequinone,2,5-dinitrophenanthrenequinone, 2-aminophenanthrenequinone,2,7-diaminophenanthrenequinone, 3,6-diaminophenanthrenequinone,2,5-diaminophenanthrenequinone, 2-oxyphenanthrene-1,4-quinone,3-oxyphenanthrenequinone, 2-oxyretenequinone, 3-oxyretenequinone,6-oxyretenequinone, 2-oxy-3,4-dinitrophenanthrenequinone,2-amino-3-oxyphenanthrenequinone; and

polynuclear aromatic compounds and derivatives thereof, such aspentacene, hexacene, benzophenanthrene, benzo[a]anthracene,naphtho[2,1,a]pyrene, dibenzo[a,j]anthracene, pyrene, coronene,1,12-benzopyrene, ovalene, dibenzoanthracene, naphthacene, Terramycin,Aureomycin, rubrene, o-toluoyl-1-naphthalene, benzoanthraquinone,5,6-dioxy-5,6-dihydrobenzoanthracene, chrysene, triphenylene,dibenzonaphthacene, hexahydropyrene, perylene, 3,9-dichlorperylene,tetrachloroperylene, 3,9-dibromoperylene, 3,10-dinitroperylene,4,6-dibenzoyl-1,3-dimethylbenzene, 6,13-dihydropentacene,naphtho[2,3a]anthracene, dispirane, dibenzo[a,h]anthracene, picene,picyleneketone, picene-5,6-quinone, dibenzo[c,g]phenanthrene,benzo[a]pyrene, benzo[a]pyrene-1,6-quinone, mesobenzoanthronepericarboxylic acid anhydride, anthraceno[2,1-a]anthracene,dibenzo[a,l]naphthacene, phenanthrene[2,3-a]anthracene,naphtho[2,3-a]pyrene, dibenzo[a,h]pyrene, dibenzo[a,l]pyrene, zethrene,anthanthrene, benzo[1,12]perylene, heptacene,tetrabenzo[a,c,h,j]anthracene, tribenzo[a,i,l]pyrene,tetrahydrodimethyldinaphthyl, mesonaphthodianthrene,mesoanthrodianthrene, 2,3:8,9-dibenzocoronene, pyranthrene, and thelike.

As quinones and derivatives thereof, there may be included:

benzoquinones and derivatives thereof, such as dibenzoquinoyl disulfide,2,5-bis(phenylthio)-p-benzoquinone, bibenzoquinone, bitoluquinone,phoenicin, Oosporein, indophenol, indoaniline, Hydron Blue, indamine,Meldola's Blue, Wurster's Blue, Wurster's Red, 4,4'-diphenoquinone,4,4'-stilbenequinone, 3,5,3',5'-tetramethyl-4,4'-diphenoquinone,3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone,3,5,3',5'-tetramethyl-4,4'-stilbenequinone,3,5,3',5'-tetra-tert-butyl-4,4'-stilbenequinone;

naphthoquinones and derivatives thereof, such as 1,2-naphthoquinone,3-oxy-2,2'-binaphthyl-1,4;3',4'-diquinone, 5,6-benzoquinoxaline,1,2-benzophenazine, 2-benzoazo-1-naphthol,4-(2,4-dioxyphenyl)-1,2-dioxynaphthalene,4-(3,4,5-trioxyphenyl)-1,2-dioxynaphthalene,1,2-naphthoquinone-1-phenylimide, 1,2-benzophenoxazine,1,2-naphthoquinone-2-chloroimide, 1,2-naphthoquinone-bis-chloroimide,2-anilino-1,4-naphthoquinone-4-anil, 2-oxy-1,4-naphthoquinone-4-anil,1,2-naphthoquinone-1-oxime benzoate, 1,2-naphthoquinone-1-oxime methylether, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol,naphtho[1',2':3,4]furazane, 1,2-naphthoquinone-2-oxime benzoate,1,2-naphthoquinone-2-oxime methyl ether,3-anilino-1,2;8,9-dibenzophenazine, Naphthyl Blue, Naphthyl Violet,1,2;5,6-dibenzophenazine, naphtho[1',2':3,4]furazane-2-oxide,triphthaloylbenzene, hexaoxynaphthalene anhydride,2,2'-binaphthyl-1,4;1',4'-diquinone,1',4'-dioxynaphtho(2',3':3,4)pyrazole,4,7-dioxy-3,3-diphenyl-5,6-benzindiazene,2-diphenylmethyl-1,4-naphthoquinone,methylnaphtho[2',3':4,5]triazole-1',4'-quinone,1,2,4-triacetoxynaphthalene, 1,4-naphthoquinonephenylimide,1,4-naphthoquinone-mono(p-dimethylaminoanil),1,4-naphthoquinonealkylimide, 4-nitroso-1-naphthol, phenylcarbamate,4-nitroso-1-naphthylamine, 4-benzhydryl-1,2-naphthoquinone,2-benzhydryl-1,4-naphthoquinone,3-benzhydryl-2-methyl-1,4-naphthoquinone, 3-geranyl-2-methyl-1,4-naphthoquinone,3-farnesyl-2-methyl-1,4-naphthoquinone,2-methyl-3-phytyl-1,4-naphthoquinone, Vitamin K1, Vitamin K2,3-allyl-2,6-dimethyl-1,4-naphthoquinone,2,6-dimethyl-3-phytyl-1,4-naphthoquinone,2,3-diallyl-6,7-dimethyl-1,4-naphthoquinone,2-phenyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone,2,6-dimethyl-3-phenyl-1,4-naphthoquinone,3-benzyl-2-methyl-1,4-naphthoquinone,2-methyl-3-(β-phenylethyl)-1,4-naphthoquinone,3-cinnamyl-2-methyl-1,4-naphthoquinone, 2-benzhydryl-1,4-naphthoquinone,4,7-diketo-8-diphenylmethyl-4,7,8,9-tetrahydro-5,6-benzindiazene,2-methyl-3-diphenylmethyl-1,4-naphthoquinone, 2,3-diphenyl-1-naphthol,naphtho[2',3':3,4]-pyrazole-1',4'-quinone,3,4-dichloro-1,2-benzophenazine, 2-iodo-1,4-naphthoquinone,1,4,5,8-tetraoxy-2,3;6,7-dibenzothianthrene,5,8-dioxy-2,3;6,7-dibenzothianthrene-1,4-quinone,2,3-diphenoxy-1,4-naphthoquinone,dinaphtho[2',3':2,3][1",2":5,4]furan-1',4'-quinone,2,3,5,8-tetrachloro-1,4-naphthoquinone,N,N'-bis-(1,4-naphthoquinone-2-yl)-benzidine,2-anilino-1,4-naphthoquinone-4-anil,4-anilino-1,2-naphthoquinone-2-anil, phenylrosindarine,2-anilino-1,4-naphthoquinone-4-(p-dimethylaminoanil),2-anilino-1,4-naphthoquinonedianil,2-anilino-3-phenyl-1,4-naphthoquinone,2-anilino-3-bromo-1,4-naphthoquinone,2-anilino-4-chloro-1,4-naphthoquinone, 2,3-dianilino-1,4-naphthoquinone,2,3-dianilino-1,4-naphthoquinonedianil, nitrosoaminonaphthoquinone,3-chloro-2-phenylnitrosoamino-1,4-naphthoquinone,phenyl-bis-(3-anilino-1,4-naphthoquinone-2-yl)amine,3-chloro-2-(p-tolylnitrosoamino)-1,4-naphthoquinone,2,7-dioxy-1-nitrosonaphthalene, 4-benzeneazo-1,3-dioxynaphthalene,di-(3-oxy-1,4-naphthoquinonyl-2-)-methane, anhydroalkannin,diquinoxalino[2',3':1,2:2",3":3,4]-naphthalene, 3,4-phthaloylfurazane;and

anthraquinones and derivatives thereof, such as 1,2-anthraquinone,2,3-anthraquinone, 1,4-anthraquinone, 9,10-anthraquinone,1,5-anthraquinone, 2,6-anthraquinone, 1,10-anthraquinone,9,9-bis(p-oxyphenyl)anthrone, anthraquinone bisdiphenylmethide,bisphenylhydrazone, benzanthrone, anthrahydroquinone,β-ethylanthraquinone, 1,3,5,7-tetramethylanthraquinone,2,2'-dianthraquinonylethane, 2,2'-dianthraquinonylethylene,1,2,3-trioxyanthraquinone, anthrachrysone, erythrooxyanthraquinone,alizarin, quinizarin, anthrarufin, chrysazin, hystazarin, anthraflavin,isoanthraflavin, anthragallol, purprin, oxyanthrarufin, anthrapurpin,oxychrysazin, oxyflavopurpurin, Rufiopin, quinazarin,alizarinpentacyanine, rufigallol, Anthracene Blue WR,alizarinhexacyanine, 2-chloroquiniazrin, 1-nitroanthraquinone,2,4,6,8-tetrabromoanthrachrysone, 3-aminoanthrapurpurin,1,8-dinitroanthraquinone, α-aminoanthraquinone, 1,1'-dianthraquinonyl,dianthraquinoneimide, 1,4-dimethylaminoanthraquinone,5-amino-1-nitro-6,8-dibromoanthraquinone,1,5-tetramethyldiamino-4,8-dinitroanthraquinone, anthraquinoneacridone,bis-N-(2-oxyanthraquinolyl)-p-phenylenediamine, leucoquinazarin,Quinazarin Green, 1-amino-2,4-dibromoanthraquinone,1,4-diacylaminoanthraquinone, anthraquinone-β-aldehyde, o-diazine,6,7-phthaloyl-1,9-benzanthrone, oxynitrosoanthraquinone,1,1'-dianthraquinolyl, azoxyanthraquinone, 8-chloropyrazoleanthrone,2,6-dihydrazinoanthraquinone, anthraquinone diazonium salt,β-anthraquinonehydrazine, azoxyanthraquinone, pyrazoleanthrone,1-(anthraquin-2-yl)-3-methylpyrazolone, 1-hydroxylaminoanthraquinone,1,5-dihydroxylaminoanthraquinone, 1-nitrosoanthraquinone,1-hydrazinoanthraquinone, 1,5-dihydrazinoanthraquinone,1-azidoanthraquinone, 2-azidoanthraquinone,anthraquinonemethylsulfoxide, 1,4-dirhodaneanthraquinone,β,β'-dianthraquinolyl sulfide, anthraquinonesulphenyl chloride,2,2'-dianthraquinonyl, 1,1'-dianthraquinonyl, helianthrone,mesobenzodianthrone, 2,2'-diamino-1,1'-dianthraquinolyl, flavanthrone,2,2'-dianthryl, mesonaphthodianthrone, 1,1'-dianthraquinolylamine,quinizarinquinone, hystazarinquinone, alizarinquinone,6-oxyquinizarinquinone, and the like.

Further, as the non-benzene type aromatic compounds, there may beincluded, for example, azulene, cyclodecapentane, cyclotetradecaheptane,cyclooctadecanonaene, cyclotetracosadodecaene, heptalene, fulvalene,sesqui-fluvalene, heptafluvalene, perinaphthene,indeno[2,1-a]perinaphthene, debenzo[bf]oxepine, dibenzo[bf]thiepine,indolizine, cyclo[3,2,2]azine, 4,5-benzotropolone, 3,4-benzotropolone,5H-benzocycloheptene, 7H-benzocycloheptene, colchicine, colchiceine,colchinol methyl ether, ditropyl ether, ditropyl sulfide,cyclopentadienyltropylidene, benzoazulene, carbinol, 4,5-benzotropolone,2-phenyltropone, naphthocycloheptadienone, naphtotropone,tribenzotropone, 1-amino-1,3-dicyanoazulene, benzoylhydrazone,3-phenyl-1-oxaazuranone-2,2-benzyltropone, 3-methyl-2-phenyltropone,2,7-diphenyltropone, 2-(α-naphthyl)tropone,2,7-tetramethylene-4,5benzotropone, 2,7-diphenyl-4,5-benzotropone,naphtho[2',3'-4,5]tropone, naphtho[2',1'-2,3]tropone, dibenzosuberane,naphtho[1',2'-2,3]tropone, dibenzosuberol, 4-oxy-2phenyltropone,4,5,7-tribomo-2-phenyltropone, 3,5'-ditropolone,3-(p-methoxyphenyl)tropolone, 4-oxy-2-phenyltropone,3-(α-naphthyl)tropolone, 3,4-diphenyltropolone, 3,7-dibenzyltropolone,4-(γ-phenylpropyl)tropolone, 3,5'-bitropolonyl,4-(p-nitrostyryl)tropolone methyl ether, 2-amino-1,3-dicyanoazurene,benzo[b]tropothiazine, 5-bromo-2-phenyltropone,4-bromo-2,7-diphenyltropone, diphenylbiphenylcarbinol, thiazinotropone,and the like.

Next, typical examples of the heterocyclic compounds having 5 or moreconjugated π bonds include the following compounds.

First, as the oxygen-containing heterocyclic compounds, there may beincluded:

furan and derivatives threreof, such as 2,5-diphenylfuran,2-phenylfuran, 3-methyl-diphenylfuran, lepidene, pyridoxine,2,4-diphenylfuran;

benzofuran, isobenzofuran, dibenzofuran and derivatives thereof, such asdibenzofuran, furano[2',3'-7,8]flavone, egonol, Euparin,1,3-diphenylisobenzofuran, tetraphenyl glycol, tetraphenylphthalan,9-phenylanthracene, o-oxymethyltriphenylcarbinol,3,3'-diphenylphthalide, 1-phenylphthalan, 1,1-phenylphthalan,3,3-diphenylphthalide, rubrene, α-sorinine, dibenzofuran,2,2'-dioxybiphenyl, 2,2'-diaminobiphenyl, phenazone, dibenzoquinone,2-hydroxybenzofuran, 2-methylbenzofuran, benzo[a]benzofuran,benzo[b]benzofuran, dibenzo[a,f]dibenzofuran, dibenzo[c,d]dibenzofuran,dibenzo[c,e]dibenzofuran, bis(2-dibenzofuryl), bis(3-dibenzofuryl);

pyran and pyrone derivatives, such as 2-p-oxyphenyl-4,6-diphenylpyryliumferrichloride, anhydrobase, benzopyran,4-p-oxyphenyl-2,6-diphenylpyrylium ferrichloride, 6-phenylcoumarin;

chromenol and chromene derivatives, such as6-methyl-2,3-diphenylchromone,6-methyl-2,3-diphenyl-4-(p-tolyl)-1,4-benzopyran-4-ol, chromanol,γ-chromene, oxychmarone, chromene, cyanizine chloride, fisetin,6-oxy-3-methoxy-5,7-dimethylflavirium chloride,4,4'-diflavilene-3,3'-oxide, chrysinidine, apigenidin, rotoflavinidine,lutosonidine, galanginidine, fisenidine, molinidine, flavoneimine,peralgonidin, cyanidin, delphinidin, petunidin, syringidin, hirsutidin,apigeninidin, carajurin, dracorhodin, dracorubin;

flavone, flavonol and isoflavon derivatives, such as flavonol, flavone,fukugetin;

coumarin and isocoumarin derivatives, such as 7-oxy-3,4-benzocoumarin,dicoumarol, angelicin, psoralen, bergapten, bergaptol, xanthotoxin,xanthotoxal, isopimpinellin, pimpinellin, oroselol, oroselone,peucedanin, oxypeucedanin, ostruthol, medakenine, nodakenetin, seselin,xanthyletin, xanthoxyletin; and

xanthone and related compounds; such as dixanthylene, 9-phenylxanthene,isoxanthone, 1,2,7,8-dibenzoxanthene, 3,9-diphenylxanthene,9,9-diphenylxanthene, and the like.

Next, the nitrogen-containing heterocyclic compounds may include:

pyrroles, such as 1-phenylpyrrole, 5-phenylpyrrole-2-aldehyde,phenyl-2-pyrrylketoneoxime, 2-phenylpyrrole, 2-methyl-1-phenylpyrrole,2-methyl-4-phenylpyrrole, 2-methyl-5-phenylpyrrole,3-methyl-5-phenylpyrrole, 2,4-diphenylpyrrole, 2,5-diphenylpyrrole,2,3-diphenylpyrrole, 2,3,5-triphenylpyrrole, 1,2,3,5-tetraphenylpyrrole,2,3,4,5-tetraphenylpyrrole, diphenyl-2-pyrrolylcarbinol,pyrrolecyclotrimethyne dye, pyrrolepolymethylene dye, biliverdin,bilirubin, prodigiosin, stercobilin;

indoles, such as 5,7-dichloro-2-phenylindole, 7-chloro-2-phenylindole,5,7-dibromo-2-phenylindole, 7-bromo-5-chloro-2-phenylindole,2-(3'-indolyl)-3-isonitroindolenine, Roseindole, Triptophan Blue,Indolo[3,2-c]quinoline, indolo[1,2-c]quinazoline, 2-phenylindole,3-nitro-2-phenylindole, 3-phenylindole, N-methyl-3-phenylindole,3-(o-nitrophenyl)indole, 2,3-diphenylindole, 3-triphenylmethylindole,2-methyl-3-triphenylmethylindole, 2-phenyl-3-triphenylmethylindole,2-(1-naphthyl)-3-triphenylmethylindole,2-(2-naphthyl)-3-triphenylmethylindole, 3,3'-diindolyl, 3,2'-diindolyl,3,3'-dehydrodiindole, Roseindole, 3-nitroso-2-phenylindole,3-nitro-2-phenylindole, 2-methyl-3-phenylazoindole,2-phenyl-3-phenylazoindole, 6-oxy-3-phenylindole, triptophan,4,5-benzotriptophan, 6,7-benzotriptophan, violasein;

oxoderivatives of indole, such as 3-(4-ethoxy-1-naphthyl)oxyindole,indophenine, indigoazine, indigoyellow 3G;

isoindoles, such as 1-chloro-4-methylphthalazine,1-benzilidenephthalimidine, 2-methyl-3-phenylphthalimidine,2-methyl-1,3-diphenylisoindole, 2,5-diphenylisoindole, β-isoindigo,dimethylimino-β-isoindigo;

carbazoles, such as 1-phenyl-1,2,3-benzotriazole, 2,2'-diaminodiphenyl,1,1'-dicarbazole;

porphyrins, such as porphyrazine, magnesium octamethyltetraazaporphyrin,azadipyromethine, phthalocyanine, diazacoproporphyrin, porphine,mesotetraphenylporphyrin, chlorophyll-b, chlorophyll-a;

oxazoles, such as 2-phenyloxazole, 4-phenyloxazole, 5-phenyloxazole,2-methyl-4-phenyloxazole, 2-methyl-5-phenyloxazole,4-methyl-2-phenyloxazole, 5-methyl-2-phenyloxazole,4,5-dimethyl-2-phenyloxazole, 2,4-diphenyloxazole, 2,5-diphenyloxazole,4,5-diphenyloxazole, 2-methyl-4,5-diphenyloxazole,2,4,5-triphenyloxazole, 2-(o-nitrophenyl)oxazole,2-(p-nitrophenyl)oxazole, 2-amino-5-phenyloxazole,2-(p-aminophenyl)oxazole, 2-(o-aminophenyl)oxazole,4,5-dimethyl-2-phenyloxidooxazole, 4-methyl-2,5-diphenyloxidooxazole,2,4,5-triphenyloxidooxazole,4-(o-methoxycarbonylbenzal)-2-phenyl-5-oxazolone, oxacarbocyanine dye,phenanthrooxazole;

isooxazoles, such as 4-nitro-3-phenylisooxazole,5-amino-3-methyl-4-phenylisooxazole, 5-benzoyl-3,4-diphenylisooxazole;

thiazoles, such as 4-phenylthiazole, 5-phenylthiazole,5-(p-fluorophenyl)thiazole, 2-methyl-4-phenylthiazole,4-methyl-5-phenylthiazole, 5-methyl-4-phenylthiazole,4,5-diphenylthiazole, 2-methyl-4,5-diphenylthiazole,1,4-bis(4-methyl-2-thiazolyl)benzene,p,p'-bis(4-methyl-2-thiazolyl)biphenyl, 2-amino-4-phenylthiazole,2-amino-5-phenylthiazole, 2-amino-4,5-diphenylthiazole,2-phenylazothiazole, 2-amino-4-methyl-5-phenylazothiazole,4-methyl-2-phenylazothiazole, α-naphthothiazole, β-naphthothiazole,naphtho[2,3]thiazole, naphtho[1,2]thiazole, 2-methyl[1,2]thiazole,2-phenylnaphtho[1,2]thiazole, 2-methylnaphtho[2,1]thiazole,4-bromo-2-phenylnaphtho[2,3]thiazole, 2-oxynaphtho[2,1]thiazole,2-aminonaphtho[1,2]thiazole, 2-aminonaphtho[2,1]thiazole,2-mercaptonaphtho[1,2]thiazole, 2-mercaptonaphtho[2,1]thiazole;

imidazoles, such as 2-phenylimidazole, 4-phenylimidazole,4-methyl-2-phenylimidazole, 2,4-diphenylimidazole,4,5-diphenylimidazole, 2,4,5-triphenylimidazole,2-bromo-4-phenylimidazole, 5-chloro-1-ethyl-2-phenylimidazole,5-chloro-1,2-diphenylimidazole, 2-phenylazoimidazole,2-methyl-4-phenylazoimidazole, 2-(o-aminophenyl)benzoimidazole;

pyrazoles, such as 3-phenylpyrazole, 5-phenylpyrazole, 4-phenylpyrazole,1-methyl-3-phenylpyrazole, 1-methyl-5-phenylpyrazole,3-methyl-5-phenylpyrazole, 1,3-dephenylpyrazole, 1,5-diphenylpyrazole,1,3,4-triphenylpyrazole, 1,3,5-triphenylpyrazole,1,4,5-triphenylpyrazole, 5-amino-3-phenylpyrazole,3-amino-5-phenylpyrazole, 5-methyl-1,3-diphenylpyrazole-4-aldehyde,3,5-diacetyl-4-phenylpyrazole, 4-benzoyl-1,5-diphenylpyrazole;

oxadiazoles, such as 3-phenylfurazane, 3,4-diphenylfurazane,naphtho[1,2]furazane, phenylfuroxane,3-methyl-5-phenyl-1,2,4-oxadiazole, 2,5'-diphenyl-1,3,4-oxadiazole;

thiadiazoles, such as 5-phenyl-1,2,3-thiadiazole,2-phenyl-1,3,4-thiadiazole, 5,5'-diphenyl-2,2'-bis(1,3,4-thiadiazole),2-oxy-5-phenyl-1,3,4-thiadiazole,2-methylsulfonyl-5-phenyl-1,3,4-thiadiazole;

triazoles, such as 2-phenyl-1,2,3-triazole,5-(p-aminophenyl)-3-mercapto-1,2,4-triazole;

tetrazoles, such as 5-phenyltetrazole, 1,5-diphenyltetrazole,1-oxy-5-phenyltetrazole, 1-amino-5-phenyltetrazole;

pyridine related compounds, such as 2-phenylpyridine, 2,2'-dipyridyl,2-chloro-6-phenylpyridine, 2,6-dichloro-3-phenylpyridine,2,2'-azopyridine, 3,3'-azopyridine, benzene-4-azopyridine,5-chloro-2,2'-azopyridine, 5,5'-dichloro-2,2'-azopyridine,4-pyridylazoresorcin, 4-pyridyl-m-phenylenediamine,3-pyridyl-m-phenylenediamine;

quinoline and related compounds, such as quinoline, quinaldine,quinaldine-N-oxide, ethylquinoline, 2-phenylquinoline,3-methylquinoline, 3-phenylquinoline, 4-methylquinoline,4-phenylquinoline, 6-methylquinoline, 6-ethylquinoline,6-phenylquinoline, 2,4-dimethylquinoline, 2,4-diphenylquinoline,quinoline-4-methanol, quinoline[6,5-f]quinoline, quinophthalone,flavaaniline, Quinoline Blue, Ethyl Red, pinacyanol, naphthocyanol,cryptocyanine, xenocyanine, azacyanine, 6,6'-octahydroquinone,Besthorn's red, 2,3'-biquinoline, 2,5'-biquinoline, 2,6'-biquinoline,2,7'-biquinoline, 3,3'-biquinoline, 4,5'-biquinoline, 4,6'-biquinoline,5,5'-biquinoline, 6,6'-biquinoline, 6,7'-biquinoline, 6,8'-biquinoline,7,7'-biquinoline, 8,8'-biquinoline, 2-fluoroquinoline,3-fluoroquinoline, 4-fluoroquinoline, 5-fluoroquinoline,6-fluoroquinoline, 7-fluoroquinoline, 8-fluoroquinoline,3-bromoquinoline, 4-chloroquinoline, 2,4-dichlorquinoline,3-nitroquinoline, 4-nitroquinoline, 2,3-quinolinediol,quinoline-2-thiol, 2-oxyquinoline-3-thiol, 2-aminoquinoline,8-aminoquinoline, 2-hydraziquinoline, pyroloquinoline,thiazoloquinoline, pyrimido[4,5-b]quinoline, benzo[f]quinoline;

isoquinoline and related compounds, such as 1-methylisoquinoline,3-bromomethylisoquinoline, 1-phenylisoquinoline, 4-phenylisoquinoline,1,1'-biisoquinoline, 5,5'-biisoquinoline, 1-chloroisoquinoline,5-iodoisoquinoline, 5-bromoisoquinoline, 5-nitroisoquinoline,isoquinoline-1,3-diol, 6,7-methylenedioxyisoquinoline,1-aminoisoquinoline, 1-cyanoisoquinoline,1-phenylbenzo[g]3,4-dihydroisoquinoline,3-(p-aminophenyl)-5,6-dihydro-8,9-dimethoxyimidazo[5,1-a]isoquinoline;

acridine and related compounds, such as acridine, 1-methylacridine,9-phenylacridine, 9-(3-pyridinyl)acridine, 2-chloroacridine,2-bromoacridine, 2-cridinol, acridine-3,6-diol, 4-methoxyacridine,9-phenoxyacridine, 1-nitroacridine, 4-aminoacridine, 1-aminoacridine,9-phenylaminoacridine, 9-oxyacridine, chrysaniline, acriflavine,3,6-diamino-4,5-dimethylacridine, acrynol;

phenanthridines, such as 3,4-benzoquinoline, 6-methylphenanthridine,6-aminomethylphenanthridine, 6-phenylphenanthridine,6-chlorophenanthridine, 6-bromophenanthridine, 6-nitrophenanthridine,1-aminophenanthridine, 3-oxyphenanthridinone;

anthrazolines, such as pyrido[2,3-g]quinoline,2,7-diphenyl[2,3-g]quinoline, 2,8-diphenylpyrido[3,2-g]quinoline;

phenanthroline and related compounds, such as 1,7-phenanthroline,1,10-phenanthroline, 4,7-phenanthroline, 8-methyl-1,7-phenanthroline,4,10-dioxy-1,7-phenanthroline, 3,5-dichloro-1,10-phenanthroline,2-amino-1,10-phenanthroline, 5-oxy-4,7-phenanthroline,5-amino-4,7-phenanthroline;

pyridoindoles, such as 1,9-pyridoindole, 2,9-pyridoindole,4,9-pyridoindole;

naphthyridine and related compounds, such as 1,5-naphthyridine,1,7-naphthyridine, 1,8-naphthyridine, 1,6-naphthyridine,2,6-naphthyridine, 2,7-naphthyridine, 1,5-naphthyridine-4-ol,3-amino-1,5-naphthyridine, 2-amino-1,5-naphthyridine,2-oxy-1,7-naphthyridine;

oxazine and related compounds such as phenoxyazinone, resazurin,carocyanin, Nile Blue A, Meldora's Blue, Brilliant Cresyl Blue;

thiazine and related compounds, such aso-benzaminophenyl-β-phenoxycarbonylethyl sulfide, phenothiazine,nitrophenothiazine, 3-chloro-10-ethylphenothiazine,4-amino-4'-anilinodiphenyl disulfide,2-chloro-10-(3-dimethylaminopropyl)phenothiazine, chloropromazine,10-(2-dimethylamino-1-propyl)phenothiazine hydrochloride,10-[2-(1-pyrrolidyl)ethyl]phenothiazine hydrochloride,10-[1-methyl-3-piperidylmethyl]phenothiazine,2-acetyl-10-(3-dimethylaminopropyl)phenothiazine, Methylene Blue;

pyridazine and related compounds, such as cinnoline, 3-methylcinnoline,4-chlorocinnoline, 3-bromocinnoline, 4-cinnolinol, 4-aminocinnoline,phthalazine, 4-ethyl-2-phenylphthalazinone, phthalazine thiol,1(2H)phthalazinone, 3-phenylpseudophthalazine,4-methyl-3-phenylpseudophthalazine, 2,3-dihydro-1,4-phthalazinedione;

pyrimidine and related compounds, such as 2-cinnamethylpyrimidine,4,6-dimethyl-2-phenylpyrimidine, 2,4,6-triphenylpyrimidine, alloxantin,2,6-dioxy-4-phenylpyrimidine, 4,6-dioxy-2-phenylpyrimidine,5-chloro-4,6-dioxy-2-phenylpyrimidine, sulfadiazine, sulfisomidine,thonzylamine hydrochloride, Vitamin B1, thiochrome, co-carboxylase,allomycin, 6-(2-furfuryl)aminopurine, pteridine, 2,4-pterine diol,2-amino-6-methyl-4-pteridinol, xanthopterine, leucopterine,isoxanthopterine, quinazoline, 4-chloroquinazoline,2,4-dichloroquinazoline, 4-quinazoline, 2,3-diphenyl-4-quinazoline;

pyrazine related compounds, such as 3,6-diphenylpyrazinol, quinoxaline,2-methylquinoxaline, 2,3-dimethylquinoxaline, 2-chloroquinoxaline,2,3-dichloroquinoxaline, 2-(o-aminoaniline)quinoxaline,N,N'-diphenyl-2,3-piperazione, 2-quinoxalinol, 2,3-quinoxaline diol,2-aminoquinoxaline, 2,3-diaminoquinoxaline,methylquinoxaline-2-carboxylic acid ester,2-(d-arabotetraoxybutyl)quinoxaline, flavazole, glucazidone, phenazine,phenazine-5-oxide, phenazine-5,10-dioxide,5-methylphenazinium-methylsulfate,10-methyl-5,10-dihydro-2-phenazinecarbonitrile, 2-phenazinecarbonitrile,1-phenazinol, 1-methoxyphenazine, 2-phenazinol,1,6-dioxyphenazine-5,10-dioxide, 1-aminophenazine, 2-aminophenazine,2,3-diaminophenazine, Neutral Red, 5,10-dihydrophenazine,5-methyl-5,10-dihydrophenazine, 1,2,3,4-tetrahydrophenazine;

tri- and tetra-hetero six-membered cyclic compounds, such as2,4,6-triphenyl-s-triazine, 2,4-dichloro-6-o-chloroaniline-s-triazine,5,6-diphenyl-as-triazine, 2,6-diphenyl-2,3,4,5-tetrahydro-as-triazine,5,6-diphenyl-as-triazine-3-ol, 1,2,4-benzotriazine,1,2,4-benzotriazine-3-ol, 3-phenyl-1,2,3-benzotriazine-4-(3H)-one,1,2,3-benzotriazine-4-ol, 1,2,3-benzotriazine-4-thiol,3-amino-1,2,3-benzotriazine, 2,3-diphenylosotetrazine,5,6-dimethyl-2,3-diphenylosotetrazine, 5-cyano-2,3-diphenylosotetrazine,5,6-dibenzoyl-2,3-diphenylosotetrazine,2,3-dibenzoyl-5-methylosotetrazine,2,3-dibenzoyl-5,6-dimethylosotetrazine,2,3-dibenzoyl-5,6-diphenylosotetrazine,2,3-bis(2,4-dichlorophenyl)-5,6-diphenyl-1,2,3,4-tetrahydro-ν-tetrazine,1,2,3,4-tetraethoxycarbonyl-5,5-diphenyl-1,2,3,4,5,6-hexahydro-ν-tetrazine,7-methyl-2-(4-methylphenyl)-1,2-dihydrobenzotetrazine,3,6-diphenyl-1,2-dihydro-s-tetrazine,1,3-diphenyl-1,4,5,6-tetrahydro-s-tetrazine,3,3,6,6-tetraphenyl-1,2,3,6-tetrahydro-s-tetrazine, and the like.

Further, the sulfur-containing heterocyclic compounds may include:

sulfur-containing heterocyclic compounds, such as 2-phenylthiophene,2,4-diphenylthiophene, 2,3,4,5-tetraphenylthiophene, metaphenylenehydrochloride, metapyrylene hydrochloride, chlorothene citrate,thenyldiamine hydrochloride, α-quinquithienyl, α-sexyithienyl;

fused thiophene type compounds, such as 3,3'-diiminothioindigo,indigoron, dihydronaphtho[2,1-b]thianaphthene,1,3-diphenylisothianaphthene, dibenzothiophene, 2-nitrodibenzothiophene,aminodibenzothiophene, 2,8-diaminodibenzothiophene,dibenzothiophene-5-dioxide, 4-oxydibenzothiophene,2,8-dioxydibenzothiophene, 2-chlorodibenzothiophene,1-bromodibenzothiophene, 2,8-dibromodibenzothiophene,2-iodo-dibenzothiophene, 2-acetyldibenzothiophene,2,8-diacetyldibenzothiophene, naphthothiophene, 3-oxythiophanthrene,2,3-thiophanthrene, naphtho[2,3-c]thiophene, naphtho[1,2-b]thiophene,naphtho[2,1-b]thiophene, naphtho[1,2-c]thiophene,1,2-naphtho[2,1-b]thiophenequinone,1-oxy-2-naphtho[2,1-b]thiophenealdehyde, naphtho[1,2-c]thiophene,2H-naphtho[1,8]thiophene, benzo[b]thiophanthrene,6,11-benzo[b]thiophanthraquinone, benzo[g]thiophanthrene,4,5-benzothiophanthrene, 8,9-benzothiophanthrene;

five-membered monocyclic compounds containing 2 hetero atoms, such as5-phenyl-1,2-dithiol-3-thione, 3,4-dihydronaphtho-2,1-trithione,thiaflavone, thiacoumarin, thiaxanthene, thiaxanthohydrol, thiaxanthone,Milacil D, bisthiaxanthylene;

six-membered cyclic compound having two or more hetero atoms, such as2,5-diphenyl-1,4-dithiadiene, thiophenealdehyde, thianthrene,2,7-dimethylthianthrene, 1-thianthrenyl lithium, 1-chlorothianthrene,phenoxthine, 2-vinylphenoxthine, 2-aminophenoxthine, 2-nitrophenoxthine,3,7-dinitrophenoxthine, 10,10-diphenylphenoxthine,2,5-diphenylthiophene, and the like.

Further, other useful compounds may include:

dicyclic compounds having commonly a nitrogen atom, such as cinchonine,2-phenylpyrrocoline, 3-ethyl-2-phenylpyrrocoline,3-benzyl-2-phenylpyrrocoline, 3-nitroso-2-phenylpyrrocoline,2:3-benzopyrrocoline, 1,5,8-trimethyl-2:3-benzopyrrocoline,1-ethyl-5,8-dimethyl-2:3-benzopyrrocoline,1,8-dimethyl-2:3-benzopyrrocoline, 3-phenyl-7:8-benzopyrrocoline,cyclo[3.3.3]azine, cyclo[3.2.2]azine, 2-phenylcyclo[3.2.2]azine,2,3-diphenylcyclo[3.2.2]azine, tricycladine, 7-methylbenzo[a]quinoliniumbromide, 7-phenylbenzo[a]quinolidinium bromide, benzo[b]quinolidiniumsalt, tetrahydro-Ψ-berberine, tetrahydroberberine, laudanosoline,tetrahydro-2,3,9,10-tetraoxy-7-methyldibenzopyrrocolium chloride,homolaudanosoline, octadehydromatrine, canadinemethoiodide,tetrahydropalmatinemethoiodide;

alkaloids, such as nicotyrine, 3',2-dipyridyl, cusparine, galipoline,1-methyl-2-quinolone, casimiroin, 2-pentylquinoline,4-oxy-2-pentylquinoline, 4-methoxy-2-pentylquinoline,1-methyl-2-pentyl-4-quinoline, 4-methoxy-2-phenylquinoline,7-methoxy-1-methyl-2-phenyl-4-quinoline, cuspareine, dictamnine,skimmianine, evolitrine, maclurin, kokusagine, kokusaginine,maculosidine, flindersiamine, evoxoidine, evoxine, evolatine,acronycidine, medicosmine, acronidine, γ-fagarine, cinchonin, quininone,quinotoxin, N-bromoquinotoxin, dihydrocinchonicine, heteroquinine,evoxantidine, xanthoquinoline, 1,3-dimethoxy-10-methylacridone,evoxanthine, xanthevodine, melicopine, melicopidine, melicopicine,acronycine, flindersine, papaverin, papaveraldine, laudanosine,laudanine, codamine, protopapaverine, almepavine,4,4',5-trimethoxy-2-vinylstilbene, coclaurine, d-isococlaurine,neprotin, corpaverine, phellodendrine, magnocurarine, coclanoline,narcotin, narcotoline, aponarceine, cinchonin, cinchotoxine,dihydrohydrastine, bicuculline, adlumidine, corlumidine, cordrastine,magnolamine, berbamine, o-methylberbamine, etc.

Among the conjugated π bond compounds described above, preferred are theones having at least one amino group. Particularly preferred suchcompounds include, for example, aminonaphthalenes such asdiaminonaphthalenes, triaminonaphthalenes and tetraaminonaphthalenes,1,4-diaminoanthracens, 9,10-diaminophenanthrene, 2,2'-diaminodiphenyl,1,1'-diamino-2,2'-dinaphthyl, 2-amino-5-phenyl oxazole,1-aminophenanthridine, 2-amino-4-phenylthiazole,2-amino-5-phenylthiazole, 3-amino-1,5-naphtyridine,1-aminophenanthridine, aminoacridines such as 4-aminoacridine,2-aminoacridine, 1-aminoacridine and 3,6-diaminoacridine, andaminophenazines such as 1-aminophenazine, 2-aminophenazine and2,3-diaminophenazine.

In a preferred embodiment of the present invention, the scalingpreventive to be used in the present invention further contains, inaddition to at least one of dyes, pigments and conjugated π bondcompounds, at least one inorganic compounds. Although an inorganiccompound alone has no scaling preventive action, the scaling preventiveaction possessed by dyes, pigments or conjugated π bond compounds hasunexpectedly been found to be further enhanced when combined with theinorganic compound. It has also been found that this effect can furtherbe exhibited, if the chloride ion concentration in the reaction mixtureis controlled to 100 ppm or less. At a level of the chloride ionconcentration in excess of 100 ppm, the scaling preventive effect is notenough to prevent effectively scaling.

When a mixture of a dye, a pigment or a conjugated π bond compound withan inorganic compound is to be applied by coating on the inner wallsurface of a polymerizer, etc., the proportion of the both componentsmay preferably be 0.1 to 2000 parts by weight of the inorganic compound,more preferably 1 to 1000 parts by weight, per 100 parts by weight ofthe dye, pigment or conjugated π bond compound.

Such inorganic compounds may include silicic acids or silicates, such asorthosilicic acid, metasilicic acid, mesodisilicic acid, mesotrisilicicacid, mesotetrasilicic acid, sodium metasilicate, sodium orthosilicate,sodium disilicate, sodium tetrasilicate, potassium metasilicate,potassium hydrogen disilicate, lithium orthosilicate, hexalithiumorthodisilicate, water glass, 12-silicotungstic acid,iso-12-silicotungstic acid, 10-silicotungstic acid, potassium12-silicotungstate, potassium iso-12-silicotungstate, potassium10-silicotungstate, sodium 12-silicotungstate, sodiumiso-12-silicotungstate, silicomolybdic acid, potassium silicomolybdate,sodium silicomolybdate, and the like;

metal salts such as oxyacid salts, acetates, nitrates, hydroxides orhalides of metals selected from alkaline earth metals such as magnesium,calcium, barium, etc., aluminum family metals such as aluminum, etc.,tin family metals such as titanium, tin, etc., iron family metals suchas iron, nickel, etc., chromium family metals such as chromium,molybdenum, etc., manganese family metals such as manganese, etc.,copper family metals such as copper, silver, etc., platinum familymetals such as platinum; etc.;

inorganic colloids prepared by mechanical crushing, irradiation ofultrasonic wave, electrical dispersion or chemical methods, such as goldcolloid, silver colloid, sulfur colloid, colloid of ferric hydroxide,colloid of stannic acid, colloid of silicic acid, colloid of manganesedioxide, colloid of molybdenum oxide, colloid of barium sulfate, colloidof vanadium pentoxide, colloid of aluminum hydroxide, colloid of lithiumsilicate and so on.

Among the above inorganic compounds, silicates, silicic acid colloid andferric hydroxide colloid are particularly preferred.

For coating of the scaling preventive on the inner wall of apolymerizer, etc., it can be applied as such or as a coating solutionprepared by dissolving or dispersing in an appropriate solvent. Theconcentration of the scaling preventive in the coating solution isgenerally preferred to be 0.01% by weight or higher.

The solvent which may be used in preparation of the coating solution maybe water or various organic solvents, including, for example:

aliphatic hydrocarbons such as gasoline, petroleum, benzine, mineralspirit, petroleum naphtha, V.M.&P. naphtha, decalin, tetralin, p-cymene,and the like;

aromatic hydrocarbons such as benzene, toluene, xylene, and the like;

halogenated hydrocarbons such as trichloroethylene, perchloroethylene,chloroform, carbon tetrachloride, ethylene trichloride, benzenemonobromide, benzene monochloride, benzene dichloride and the like;

alcohols such as amyl alcohol, ethyl alcohol, isopropyl alcohol,2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methylalcohol, methylamyl alcohol, benzyl alcohol, butyl alcohol and the like;

ketones such as acetone, acetonylacetone, diisobutyl ketone, diethylketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone,methylcyclohexanone, methyldipropyl ketone, methyl ethyl ketone, methyln-hexyl ketone, methyl isobutyl ketone, methyl propyl ketone, mesityloxide, and the like;

esters such as acetates, butyrates, propionates, formates and the like;

alcohol esters such as butyl lactate, isopropyl lactate, ethyl lactate,ethyl oxypropionate, diethyl maleate and the like;

ketone esters such as ethyl acetoacetate, ethyl pyruvate and the like;

ethers such as isopropyl ether, ethyl ether, diethyl carbitol, diethylcellosolve, butyl ether, and the like;

ketone alcohols such as acetonylmethanol, diacetone alcohol, dihydroxylacetone, pyruvyl alcohol and the like;

ether alcohols such as isopropyl cellosolve, carbitol, glycidol,cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butylcellosolve, methyl carbitol, methyl cellosolve, triethyleneglycolmonoethyl ether and the like;

ketone ethers such as acetal ethyl ether, acetonyl-methanol ethyl ether,methyl ethoxyethyl ether, and the like;

ester ethers such as butylcarbitol acetate, butyl cellosolve acetate,carbitol acetate, cellosolve acetate, 3-methoxybutyl acetate,methylcarbitol acetate, methyl cellosolve acetate, and the like.

When organic solvents highly compatible with water are employed, watermay be added to the coating solution in an amount within the range whichdoes not impair solubility or dispersibility of the scaling preventive,whereby the coating solution can be improved in economy and safetyduring transportation and storage. Such solvents includes:

alcohols such as methyl alcohol, ethyl alcohol, allyl alcohol, n-propylalcohol, isopropyl alcohol, and the like;

ketones such as acetone, acetonylacetone, diacetone alcohol and thelike;

esters such as ethyleneglycol monomethyl ether acetate, diethyleneglycolmethyl ether acetate, monoethyl ether acetate and the like;

ethers such as dioxane, ethyleneglycol monomethyl ether, ethyleneglycolmonoethyl ether and the like;

furans such as tetrahydrofuran, furfuryl alcohol and the like;

aprotic solvents such as acetonitrile, N,N-dimethylformamide,N,N-dimethylacetamide and the like.

When the scaling preventive to be used is a water-soluble sulfonic acidtype or carboxylic acid type dye having sulfonic acid groups orcarboxylic acid groups in the form of an alkali metal salt or ammoniumsalt, water can be used as the solvent in which the preventive is to bedissolved, as disclosed in Japanese Patent Publication No. 5442/1981,whereby there is the advantage in safety and hygiene that the solvent isnon-toxic and harmless. If water is used as the solvent as describedabove, wettability of the coating solution for the inner wall of apolymerizer, etc. can be enhanced by addition of alcohols, preferably C₃-C₆ monohydric alcohols, such as n-propyl alcohol, n-butyl alcohol,iso-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol,t-amyl alcohol, iso-amyl alcohol, sec-amyl alcohol, sec-hexyl alcohol,etc., as disclosed in Japanese Patent Publication No. 5444/1981. Also,as disclosed in Japanese Patent Publication No. 5442/1981, for thepurpose of making drying of the coating solution after coating easier,an organic solvent compatible with water such as alcoholic solvents,ester solvents, ketone solvents, may be added to the coating solution.

In carrying out coating of the coating solution containing the scalingpreventive on the inner wall of a polymerizer, etc. according to theprocess of the present invention, various fixing agents can be used forenhancement of the fixing characteristic, if desired. The fixing agentmay be used according to various methods, for example, the method inwhich it is incorporated in the coating solution containing the scalingpreventive, the method in which the fixing agent or a solution thereofis previously applied on the wall surface prior to coating of thescaling preventive, followed by overlaying of the scaling preventivethereon, and the suitable method may be selected depending on the kindof the scaling preventive and the kind of the fixing agent.

Such fixing agents may include the polymeric compounds as shown below:

olefin polymers, such as polyethylene, polyethylene sulfonic acid,polypropylene, poly(1-butene), polyisobutene, polycyclopentene,polycyclopentylethylene, polycyclohexylethylene,poly(3-cyclohexyl-1-propene), poly(4-cyclohexyl-1-butene),poly(5-cyclohexyl-1-pentene), poly(cyclotrifluoroethylene),poly(tetrafluoroethylene);

diene polymers, such as polyallene, polybutadiene, polyisoprene,polychloroprene, poly(1-methoxybutadiene),poly(2-tert-butyl-1,3-butadiene), poly(cyclopentadiene),poly(1,3-cyclohexadiene), poly(dimethylfulvene),poly(4-vinyl-1-cyclohexane), poly(1,5-hexadiene),poly(1,5-cyclooctadiene), poly(bicyclo-[2,2,1]-hepta-2,5-diene),poly(5,7-dimethyl-1,6-octadiene), poly(diallylphthalate),poly(diallylmethylsilane), poly(diallylphenylphosphineoxide);

acetylene polymers, such as polyacetylene, poly(cyanoacetylene),poly(hydroxymethyl)acetylene), poly(butoxyacetylene),poly(phenylacetylene), poly(diphenyldiacetylene),poly(pyridylacetylene);

aliphatic vinyl polymers and vinylidene polymers, such as polyvinylalcohol, polyallyl alcohol, poly(vinylformal), poly(vinylacetal),poly(vinylbutyral), poly(vinylisobutyral),poly(vinylcyclohexanoneketal), poly(vinyl acetate),poly(vinylchloroacetate), poly(vinyl isobutyrate), poly(vinyl pivalate),poly(vinyl n-caproate), poly(vinyl caprylate), poly(vinyl laurate),poly(vinyl palmitate), poly(vinyl benzoate), poly(vinyl sulfate),poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl bromide),poly(vinyl methyl ether), poly(vinyl ethyl ether), poly(vinyl n-propylether), poly(vinyl isopropyl ether), poly(vinyl n-butyl ether),poly(vinyl isobutyl ether), poly(vinyl tert-butyl ether), poly(vinylneopentyl ether), poly(vinyl carbomethoxymethyl ether),poly(vinyl-2-methoxyethyl ether), poly(vinyl-2-chloroethyl ether),poly(vinyl 2,2,2-trifluoroethyl ether), poly(vinyl benzyl ether),poly(vinyl methyl ketone), poly(methyl isopropenyl ketone),poly(1-nitropropylene), poly(vinylsulfofluoride), poly(vinylsulfonicacid), poly(vinyl diphenylphosphineoxide), poly(vinyldiphenylphosphinesulfide),poly(dimethyl-2-cyano-2-propene-1-phosphonate),poly(diethyl-2-cyano-2-propene-1-phosphonate), poly(maleic anhydride);

aromatic vinyl polymers, such as polystyrene, poly(α-methylstyrene),poly(4-chlorostyrene), poly(4-bromostyrene), poly(dichlorostyrene),poly(4-methoxystyrene), poly(2,5-dimethoxystyrene),poly(vinyl-bis(1-ethoxyethyl)hydroquinone), poly(4-vinyl-phthalic acid),poly(4-vinylphenylboric acid), poly(diphenyl-4-styrylphosphine oxide),poly(diphenyl-4-styrylphosphine sulfide), poly(9-vinylanthracene),poly(4-vinylbiphenyl), poly(acenaphthylene), polyindene;

heterocyclic vinyl polymers, such as poly(N-vinylcarbazole), poly(9-Δ⁵-pentenylcarbazole), poly(9-Δ⁵ -hexenylcarbazole),poly(N-vinylpyrrolidone), poly(2-vinylpyridine), poly(4-vinylpyridine),poly(2-methyl-2-vinylpyridine), poly(2,4-dimethyl-6-vinyl-S-triazine),poly(N-vinyl-1,2,4-triazine), poly(N-vinylbenztriazole),poly(N-morpholinone-(3)), polycoumarone;

acrylic and methacrylic polymers, such as polyacrylic acid,polymethacrylic acid, poly(methyl acrylate), poly(ethyl acrylate),poly(butyl acrylate), poly(5-cyano-3-thia-phenylacrylate), poly(methylmethacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate),poly(n-butyl methacrylate), poly(isobutylmethacrylate), poly(n-hexylmethacrylate), poly(2-ethylbutyl methacrylate), poly(n-octylmethacrylate), poly(n-lauryl methacrylate), poly(4-(tert-butyl)phenylmethacrylate), poly(bornyl methacrylate), poly(β-(N-carbazyl)ethylmethacrylate), poly(tert-butyl crotonate), polyacrylonitrile,polymethacrylonitrile, polyacrylamide, poly(N,N-dimethylacrylamide),poly(N-(1,1-dimethyl-3-oxobutyl)acrylamide, poly(acrylopiperidine),poly(acrylomorpholide), poly(9-acryloylcarbazole), polymethacrylamide,polyacrolein, poly(α-methylacrolein), poly(diacryloylmethane),poly(acrylic anhydride), poly(methacrylic anhydride);

polyethers, such as polyformaldehyde, polyacetaldehyde,poly(mono-chloroacetaldehyde), polychloral, polypropionaldehyde,polyacrolein, poly(2-formyl-Δ⁵ -dihydropyrane),poly(trans-1,2-cyclohexanedicarboxyaldehyde), poly(glutardialdehyde),poly(β-methylglutardialdehyde), poly(β-phenylglutardialdehyde),poly(dimethylketene), polyacetone, poly(monobromoacetone),poly(7-oxa-bicyclo[2,2,1]heptane), poly(3-phenoxylene),poly(2,6-xylenol), poly(ethylene oxide), poly(propylene oxide),poly(cyclopentene oxide), poly(cyclohexene oxide), poly(phenylglycidylether), poly(1,2-di(epoxyethyl)benzene),poly(3,3-bis(chloromethyl)oxetane), poly(tetrahydrofuran);

polysulfides, polysulfones, such as poly(thiocarboxylfluoride),poly(ethylenedichloride-sodium tetrasulfide), poly(dichlorodiethylether-sodium disulfide), poly(dichlorodiethyl ether-sodiumtetrasulfide), poly(phenylenesulfide), poly(ethylenesulfone),poly(propylenesulfone), poly(1-butenesulfone),poly(5-norbornenesulfone), poly(styrenesulfone), poly(1-pentylsulfone),poly(1-hexylsulfone), poly(1-heptylsulfone), poly(butadienesulfone),poly(isoprenesulfone), poly(dimethylbutadienesulfone),poly(1,5-hexadienesulfone), poly(cis,cis-cyclooctadienesulfone),poly(norbornadienesulfone);

various addition polymers, such as poly(methylene diisocyanate),poly(ethylene diisocyanate), poly(trimethylene diisocyanate),poly(tetramethylene diisocyanate), poly(5-iminohydantoin),poly(perfluoroglutarodinitrile), poly(1-(perfluorobutyryl)aziridine);

formaldehyde resins, such as phenol-formaldehyde resin,melamine-formaldehyde resin, urea-formaldehyde resin,aniline-formaldehyde resin, p-toluenesulfonamide-formaldehyde resin;

polyesters, such as poly(11-oxyundecanoate), poly(hexamethylenesuccinate), poly(hexamethylene sebacate), poly(hexadecamethylenesebacate), poly(hexamethylene-α α'-dibutylsebacate), poly(octamethylenecis-hexahydroterephthalate), poly(octamethylentranshexahydroterephthalate), poly(hexamethylene maleate),poly(hexamethylene fumarate), poly(hexamethyleneacetylenedicarboxylate), poly(ethylene terephthalate), poly(p-phenyleneisophthalate), poly(4,4'-biphenylene isophthalate), poly(hexamethylenecarbonate), poly(p-phenylene carbonate), poly(m-phenylene carbonate),poly(4,4'-isopropylidenediphenylene carbonate),poly(4,4'-(2-pentylene)diphenylene carbonate),poly(1,2-bis(hydroxymethyl)carborane-adipic acid), poly(allylsulfonate),poly(hydroquinone-aryloxyphosphoryl dichloride),poly(hydroquinone-(chloromethyl)phosphoryl dichloride),poly(hydroquinone-(N-dimethyl)phosphoramidic acid)dichloride;

polyamides, such as poly(isocyanate), poly(vinylisocyanate),poly(butylisocyanate), poly(3-aminopropionic acid),poly(6-aminopropionic acid), poly(11-aminoundecanoic acid),poly(hexamethylene adipamide), poly(decamethylene adipamide),poly(3,3'-(methylimino)bistrimethylene adipamide),poly(benzidine-isophthalic acid), poly(pyrromelliticdianhydride-aromaticdiamine), poly(1,6-hexamethylene-bis(carboxyethyl)sulfide),poly(1,6-hexamethylenediamine-benzene-1,3-bis-sulfonic acid chloride),poly(trans-2,5-dimethyl-piperazine-4,4'-sulfonyl-dibenzoyl chloride),poly(bis(3-aminopropyl)phenylphosphine-adipic acid),poly(bis(3-aminopropyl)phenylphosphine-terephthalic acid),poly(bis(3-aminopropyl)methylphosphine oxide-adipic acid),poly(bis(3-aminopropyl)n-octylphosphine-adipic acid),poly(bis(3-aminopropyl)phenylphospine oxide-adipic acid),poly(hexamethylenediamine-bis(2-carboxyethylene)phenylphosphine oxide),poly(hexamethylenediamine-bis(p-carboxyphenyl)phenylphosphine oxide),poly(piperazine-bis(2-carboxyethyl)phenylphosphine oxide);

polyureas, polyurethanes, such as polyureas,poly(1,10-decamethylenediamine-1,6-hexamethylene-bis-ethylurethane),poly(diphenylmethane-4,4'-diisocyanate-4,4'-diphenylmethane),poly(toluene-2,4-diisocyanate-N,N'-bis(trimethylsilyl-p,p'-diaminodiphenylether, polyurethane, polyurethane poly(propyleneoxide) basis;

various linear condensed polymers, such as poly(diethylcarbodiimide),poly(diallylcarbodiimide), poly(di-n-butylcarbodiimide),poly(methylisopropylcarbodiimide), poly(di-n-hexylcarbodiimide),poly(diphenylcarbodiimide), poly(4,4'-diphenylenemethanecarbodiimide),poly(hexamethylenecarbodiimide), poly(1,3-xylylenecarbodiimide),poly(3-methyl-1,4-phenylenecarbodiimide),poly(2,2'-dimethyl-biphenylenecarbodiimide),poly(2,2'-dimethoxy-biphenylenecarbodiimide),poly(1,5-naphthylenecarbodiimide), poly(adipyldihydrazide-succinoylchloride), poly(adipyldihydrazide-isophthaloyl chloride),poly(isophthalicdihydrazide-terephthaloyl chloride),poly(2,5-dimethylbenzylene), poly(p-xylylene),poly(2,5-dimethylxylylene), poly(2,5-dimethoxy-p-xylylene),poly(p-xylylidene), poly(α-cyano-m-xylylidine),poly(α-cyano-p-xylylidine), poly(nitrophenylene),poly(tetramethyl-p-phenylenedimethylene),poly(2,5-dihydroxy-p-phenylenedimethylene),poly(4,4'-oxydiphenylenedimethylene),poly(2,5-dimethoxy-p-phenylenedimethylene);

heterocyclic condensed polymers, such as poly(benzoimidazole),poly(alkylene-5,5'-dibenzoimidazole),poly(allylene-5,5'-dibenzoimidazole), poly(pyromellitimide),poly(benzooxazole), poly(oxadiazole), poly(oxadiazolidine),poly(dithiazole), poly(benzothiazole),poly(1,4-xylenyl)-2-methylpiperazine), poly(quinoxaline),poly(S-triazinyleneimide);

natural polymers, modified natural polymers, such as natural rubber,cyclized rubber, hydrochloric acid rubber, chlorinated rubber,guttapercha, cellulose, methyl cellulose, ethyl cellulose, propylcellulose, butyl cellulose, allyl cellulose, benzyl cellulose,hydroxyethyl cellulose, carboxylmethyl cellulose, cyanoethyl cellulose,cellulose triformate, cellulose acetate, cellulose triacetate, cellulosetripropionate, cellulose tributyrate, cellulose tricaproate, cellulosetricarbanilate, cellulose nitrate, cellulose trinitrate, starch,amylose, amylose acetate, amylose carbanilate, amylopectin, alginicacid, chitin, glycogen, gum arabic, gum tragacanth, heparine, pectin,rosin, kopal, shellac, casein, collagen(calf-skin),collagen(ichthyocol), gelatin, peanut-protein, soybean-protein, nucleicprotein (calf thymus), nucleic protein (sperm of sea urchin),poly(sarcosine), sericin, silk, wool, zein, polyadenylic acid,deoxyribonucleic acid, ribonucleic acid;

polysiloxanes, such as polysiloxane, polydimethylsiloxane;

organic metal polymers, such as poly(bis(imidazolate)-metal(II),poly(aluminumtriisopropylateethylenediamine); and

inorganic polymers such as polymetaphosphate, and

In the process of the present invention, the above-mentioned scalingpreventive is applied on the inner wall surface of a polymerizer and theportions of the auxiliary polymerizer equipment where scales may besticked, namely the portions which monomers may come into contact withduring polymerization (including portions which monomers can possiblecontact), for example, stirring blades, stirring shaft, condenser,header, baffles, search coil, bolts, nuts, etc. Preferably, the scalingpreventive is further applied on the portions of recovery system ofunreacted monomers where scales may be sticked, for example, the innersurfaces of monomer distillation columns, condensers, monomer storagetanks, valves, etc.

The materials of the above polymerizer and portions of the auxiliarypolymerizer equipment are not particularly limited, but such a materialas stainless steel or a material applied with glass lining may beavailable. These portions where coating is to be applied shouldpreferably have a surface roughness (Rmax as defined by JIS B 0106) of10 μm or less, more preferably 5 μm or less.

The method for applying the scaling preventive on the inner surface of apolymerizer, etc. as mentioned above is not particularly limited, andmay be inclusive typically of the brush coating, spray coating, themethod of filling the polymerizer with a coating solution followed bywithdrawal thereof, and otherwise the automatic coating methods asdisclosed in Japanese Laid-open Patent Publication (Kokai) Nos.61001/1982, 36288/1980, Japanese Laid-open Patent Publication (Kohyo)Nos. 501116/1981, 501117/1981 and Japanese Laid-open Patent Publication(Kokai) No. 11303/1984.

The process of the present invention is applicable forhomopolymerization of vinyl chloride monomer and copolymerization ofvinyl chloride monomer with other vinyl monomers in an aqueous medium.The system of polymerization may be either suspension polymerization oremulsion polymerization. Vinyl monomers which can be provided forcopolymerization may be exemplified by vinyl esters such as vinylacetate, vinyl propionate, acrylic acid, methacrylic acid or theiresters or salts, maleic acid or fumaric acid, and their esters ofanhydrides, diene monomers such as butadiene, chloroprene or isoprene,further styrene, acrylonitrile, vinyldiene halide, vinyl ether, etc.

In the suspension and emulsion polymerizations, the polymerizationcatalysts generally employed are, for example, organic peroxides such ast-butylperoxyneodecanate, di-2-ethylhexylperoxydicarbonate,3,5,5-trimethylhexanoylperoxide, α-cumylperoxyneodecanoate, cumenehydroperoxide, cyclohexanoneperoxide, t-butylperoxypivalate,di-2-ethoxyethylperoxydicarbonate, benzoyl peroxide, lauroyl peroxide,2,4-dichlorobenzoyl peroxide, diisopropylperoxydicarbonate andacetylcyclohexylperoxide, etc., azo catalysts such asα,α'-azobisisobutyronitrile, α,α'-azobis-2,4-dimethylvaleronitrile,water soluble persulfates such as potassium persulfate, ammoniumpersulfate, etc. Also, as a dispersant, there may be employed, forexample, suspending agents such as natural or synthetic polymericcompounds, e.g., partially saponified product of polyvinyl acetate,polyacrylic acid, copolymer of vinyl acetate and maleic anhydride,cellulose derivative such as hydroxypropylmethyl cellulose and gelatin;emulsifiers as exemplified by nonionic emulsifiers such as sorbitanemonolaurate, sorbitane trioleate, anionic emulsifiers such as sodiumlaurylsulfonate, sodium alkylbenzenesulfonate. As other additives,fillers such as calcium carbonate, titanium oxide, etc., stabilizerssuch as tribasic lead sulfate, calcium stearate, dibutyltin laurate,dioctyltin mercaptide, etc., lubricants such as lice wax, stearic acid,cetyl alcohol, etc., plasticizers such as DOP, DBP, etc., chain transferagents such as trichloroethylene, mercaptans, etc. and pH controllersmay be added into the polymerization system. According to the process ofthe present invention, irrespectively of which catalysts, dispersants oradditives may be employed, scaling can effectively be prevented in anypolymerization system.

The present invention is described in more detail below by referring tothe following Examples, by which the scope of the present invention isnot limited.

(Note: In the following Examples, Experiment Nos. 218 to 300 areskipped.)

EXAMPLE 1

As shown in Table 1, for each experiment, a dye or a pigment wasdissolved or dispersed in a solvent, optionally with the addition of aninorganic compound or a polymeric compound as shown in the same Table toprepare a coating solution. The formulation ratio of the inorganiccompound or the polymeric compound and the concentration of the dye orpigment in the coating solution are also shown in Table 1. The coatingsolution was applied on the polished inner wall surface of a stainlesssteel polymerizer of an inner volume of 1000 liters and the portionswhich may contact with monomers such as stirrer, dried at 80° C. for 10minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 200 Kg of vinylchloride monomer, 400 Kg of deionized water, 44 g of partiallysaponified Poval, 56 g of hydroxypropylmethyl cellulose and 60 g oft-butylperoxyneodecanate, and polymerization was carried out at 52° C.for 7 hours. After completion of polymerization, the polymer was takenout and the polymerizer was washed internally with water at a flow rateof 0.1 m³ /m² hr as shown in Table 1. The above operations from coatingand charging to washing with water were conducted for each batch andthis was repeated for a maximum of 200 batches.

The chloride ion concentration in the reaction mixture duringpolymerization in each experiment was controlled by changing thecontents of the methyl chloride and hydrochloric acid componentscontained in the starting vinyl chloride monomer, the temperature of thecharged deionized water (in the range of from 10° to 80° C.) and thedegree of vacuum after charging of deionized water and the suspendingagent (-750 to -100 mmHg). Various starting vinyl monomer materials withdifferent contents of methyl chloride and hydrochloric acid wereprepared by mixing two kinds of vinyl chloride monomers, namely (1) onecontaining 40 to 50 ppm of methyl chloride and 0 to 2 ppm ofhydrochloric acid and (2) the other containing 1000 to 3000 ppm ofmethyl chloride and 1 to 10 ppm of hydrochloric acid at various weightratios within the range of from 80:100 to 20:0.

After completion of polymerization of each batch, the chloride ionconcentration in the slurry was measured according to the method definedby JIS K 0102 (1974). The average value and the maximum and minimumvalues of their measured values are shown for each experiment in Table1.

Also, scaling after completion of each batch of the 10th, 30th, 50th,100th, 150th and 200th batch was evaluated by visually according to thestandards shown below, and the amount of scales adhering (g/m²) was alsomeasured after completion of the final batch. The results are also shownin Table 1.

A: no sticking of scale

B: several percent sticking of sandy scales

C: scales sticking thinly over part of the surface (about 10% stickingpercentage)

D: scales sticking thickly over part of the surface (about 10% stickingpercentage)

E: scales sticking thinly over part of the surface (about 50% stickingpercentage)

F: scales sticking thickly over part of the surface (about 50% stickingpercentage)

G: scales sticking thinly over the entire surface

H: scales sticking thickly over the entire surface

In Table 1, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 1 and 2 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound. Also, the coating solutionemployed in Experiment Nos. 33 and 34 was prepared by dissolving onepart of sodium sulfide in 100 parts of water and adding 0.5 part of adye to the resultant solution, followed by heating at 80° C. for 30minutes.

    TABLE 1       (3) (4)  Coating Solution Cl.sup.-  conc. Time for washing Scaling (1) D     ye or pigment(a) Inorganic (a)/(b) Polymeric (a)/(c) (2) Solvent upper:     average with water after Visual evaluation (Amount attached to g/m.sup.2)      Exp.  Mixing compound weight compound weight conc.  Mixing lower:     max.-min. completion Batch No. No. Kind ratio (b) ratio (c) ratio % Kind r     atio ppm min. 10 30 50 100 150 200        1* --  --  --   --  300  60 H(1000)                350-280  2* --  --      --   --  15 " H(900)           17-12  3* Solvent Black 5  --  --  0.5     Methanol  300  " B F H(800)           350-270  4* "  --  --  " Methanol     200  " B F H(500)           250-180  5* "  --  --  " Methanol  150  " B     C F H(300)           180-130  6* "  Colloidal silica 100/50  --  0.9     Methanol  250  " B D F H(300)           280-200  7* "  " 100/150 Shellac     resin 100/50 1.5 Methanol  300  " B C F H(200)           340-270  8* "     CuCl.sub.2 100/2  --  0.5 Methanol  280  " B C F H(350)     310-250  9* --  Colloidal silica  0/100 --  0.5 Methanol  15 " H(900)            17-12  10* Solvent Black 7  FeCl.sub.2 100/5  --  0.5 Methanol     230  " B C F H(250)           280-200  11* Acid Black 2  Colloidal     silica 100/200 --  0.9 Methanol  250  " B C F H(220)           290-210     12* Basic Orange 14  Water glass 100/150 --  1.0 Water/ 90/10 230  " B C     F H(400)         Isobutyl  280-200         alcohol  13* Acid Blue     102/Basic 70/30 Orthosilicic 100/200 --  1.5 Water  260  60 B C F H(350)      Orange 14  acid       290-230  14* Basic Red 2  Fe(OH).sub.3 sol 100/50      --  1.0 Methanol  270  " B C G H(400)           320-250  15* Basic     Black 2  FeCl.sub.2 100/3  --  0.5 Methanol  230  " B C F H(300)       290-210  16* Basic Orange 2  Colloidal silica 100/100 --  1.0 Water     250  " B C F H(450)           300-220  17* Basic Brown 1  Fe(OH).sub.3     sol 100/10  --  0.5 Water 300  " B F H(400)           350-280  18* Acid     Black 2  --  --  0.5 Water  310  " B F H(600)           370-290  19*     Disperse Black 29  --  --  0.7 Acetone  265  " B F H(700)     315-245  20* Mordant Black 9  --  --  0.5 Water  285  " B F H(500)         335-265 21 Basic Black 8  --  --  0.5 Water  15 10 A A A B C D(15)             18-13 22 Basic Brown 1  --  --  0.6 Water/ 90/10 18 " A A A B C     D(16)         Isobutyl  21-26         alcohol 23 Basic Brown 1  Fe(OH).su     b.3 sol 100/10  --  0.6 Water/ 90/10 16 " A A A A A A(0.2)     Isobutyl  18-15         alcohol 24 Basic Orange 2  Colloidal silica     100/100 --  0.8 Water  13 " A A A A A A(0.5)           15-10 25 Basic     Red 32  --  --  0.3 Water  14 10 A A A B C D(18)           16-13 26     Disperse Orange 5  --  --  0.5 Acetone  10 " A A A A B C(9.5)     12-8  27 Disperse Violet 10  --  --  0.9 Acetone  11 " A A A B C D(20)             13-9  28 Disperse Black 29  --  --  1.0 Acetone  12 " A A A A B     C(7)           14-10 29 Pigment Brown 4  --  Polycyclo- 100/50 1.5     Methanol  18 " A A A A B C(8)      hexylethylene     20-16 30 Solvent     Yellow 61/ 50/50 --  --  0.8 Water/ 70/30 16 15 A A A A B C(9)  Basic     Blue 44       Methanol  18-14 31 Solvent Brown 37/ 40/60 --  --  0.6     Water/ 50/50 20 " A A A A B C(10)  Vat Blue 6       Methanol  22-18 32     Vat Orange 15  --  --  0.7 Xylene   9 " A A A A B C(7.5)           11-7     33 Vat Green 44  --  --  0.5 Water   5 " A A A A B C(6.4)           7-3     34 Vat Brown 22  --  --  0.5 Water  15 " A A A B C D(18)           17-13     35 Vat Orange 1/ 30/70 --  --  1.0 Xylene  13 " A A A A B C(10)  Vat     Blue 19         15-10 36 Basic Blue 7  NiCl.sub.2 100/20  --   1.2     Water/n- 80/20 12 " A A A A A A(0.7)         Amyl  14-11         alcohol     37 Basic Orange 14  Water glass 100/150 --  0.9 Water   9 15 A A A A A     A(0.6)           11-7  38 Pigment Blue 15  --  Polycyclo-  100/100 0.8     THF  10 " A A A A B C(9)      pentadiene     12-8  39 Pigment Red 87  --      Poly(1,3- 100/30 0.8 Acetone  13 " A A A B C D(17)      cyclo-     15-10      hexadiene 40 Solvent Blue 73  --  --  0.4 Methanol   8 10 A A     A A B C(10)           10-5  41 Solvent Red 49  --  --  0.7 Methanol 10 "     A A A A B C(11)           12-8  42 Solvent Red 49  Colloid of sulfur     100/5  --  0.7 Methanol  15 " A A A A A A(0.8)           17-13 43 Basic     Orange 15  --  --  1.3 Water  14 " A A A A B C(8)           16-12 44     Solvent Black 5  CuCl.sub.2 100/2  --  0.7 Water/ 30/70 13 " A A A A A     A(0.2)         Methanol  15-11 45 Basic Black 2  FeCl.sub.2 100/3  --     0.8 Water  15 " A A A A A A(0.3)           17-12 46 Basic Blue 3     Metasilicic acid 100/100 --  1.5 Water  17 " A A A A A A(0.5)     19-15 47 Basic Blue 9  --  --  0.8 Water  15 " A A A A B C(6.4)      17-12 48 Basic Red 13  --  --  0.4 Water/n- 50/50 16 " A A A B C D(18)            Butyl  18-13         alcohol 49 Solvent Black 5  Colloidal silica     100/50  --  0.6 Water/ 20/80 18 10 A A A A A A(0.6)         Methanol     20-15 50 Direct Orange 57  --  --  0.7 Water  15 " A A A B C D(19)         17-13 51 Direct Orange 57  Colloid of 100/10  --  0.7 Water  10 " A     A A A A A(0.9)    stannic acid       13-8  52 Direct Red 1/Direct 50/50     --  --  0.4 Water   5 " A A A A B C(7)  Blue 158         7-3 53 Direct     Green 8  --  --  0.6 Water  16 " A A A A B C(9)           18-14 54     Direct Brown 25  --  --  0.5 Water  13 " A A A B C D(15)           15-10     55 Direct Brown 25  ZnCl.sub.2 100/20  --  0.5 Water  11 " A A A A A     A(0.9)           13-9  56 Acid Yellow 11  --  --  0.8 Water  14 " A A A     B C D(18)           16-11 57 Acid Red 37  --  --  0.4 Water/n- 50/50 10     15 A A A B C D(18)         Butyl  12-7          alcohol 58 Acid Blue     60/Acid  Fe(OH).sub.3 sol 100/20  --  0.7 Water   9 " A A A A A A(0.2)     Black 7         11-6  59 Mordant Red 9  --  --  0.8 Water   7 " A A A A     B C(9)           9-4 60 Mordant Green 15  --  --  1.0 Water  18 " A A A     B C D(19)           20-15 61 Solvent Black 30  --  Poly- 100/60 1.6     Water/ 70/30 17 15 A A A A A B(2.5)      acrylamide   Methanol  19-14 62     Mordant Black 9  --  --  0.6 Water   9 " A A A A B C(10)           11-6     63 Acid Green 12  --  --  0.4 Water  18 " A A A B C D(18)     20-15 64 Acid Green 12  Co(CH.sub.3 --COO).sub.2 100/15  --  0.4 Water     15 10 A A A A A A(0.6)           18-13 65 Acid Violet 78  --  --  0.8 "     15 15 A A A B C D(15)           17-12 66 Acid Blue 151  --  Polycyclo-     100/20 0.6 Water/ 30/70 13 10 A A A A A A(0.2)      pentylethyl     Methanol  15-10 67 Solvent Red 109  --  --  0.3 Methanol  11 " A A A A A     B(2.5)           13-7  68 Acid Black 159  Metasilicic acid 100/300 --     1.6 Water/ 90/10 14 " A A A A A A(0.3)         Isobutyl  16- 11     alcohol 69 Mordant Black 13  --  --  0.8 Water  12 " A A A B C D(19)           14-9  70 Acid Red 80/ 40/60 ZnCl.sub.2 100/2  --  0.5 Water  18 "     A A A A A A(0.5)  Food Blue 1         20-15 71 Acid Blue 74  --  --  0.6     Water  19 " A A A B C D(20)           21-16 72 Acid Blue 74  Colloid of     100/20  --  0.6 "  14 " A A A A A A(0.4)    molybdenum       17-12     oxide 73 Direct Blue 86  --  --  0.8 Water  17 10 A A A B C D(15)        19-14 74 Mordant Blue 58  --   --  1.0 Water  20 " A A A B C D(17)            22-18 75 Solvent Black 3  Colloidal silica 100/50  --  0.6 Water/     20/80 14 " A A A A A A(0.4)         Methanol  16-11 76 Acid Green 9  --     --  0.5 Water  15 " A A A B C D(19)           17-12 77 Mordant Violet 15      --  --  0.7 Water  13 " A A A A B C(10)           15-10 78 Mordant     Violet 15  Al(OH).sub.3 sol 100/2  --  0.7 Water  13 " A A A A A A(0.5)              16-11 79 Pigment Green 2  --  Polyallene  100/100 2.0 Water/     50/50 14 15 A A A A B C(9)         Methanol  16-11 80 Pigment Violet 1     --  Cellulose 100/30 1.3 Water/ 20/80  9 " A A A A B C(10)      acetate      Methanol  11-6  81 Food Red 14  --  --  0.2 Water   7 " A A A B C D(20)               9-4 82 Acid Black 2  Colloidal silica 100/200 --  0.7 Water/n-     90/10  5 " A A A A A A(0.7)         Amyl  7-3         alcohol 83 Acid     Blue 59  --  --  0.5 Water  12 " A A A A A B(1.5)           14-9  84     Direct Blue 106  --  --  0.5 Water  16 " A A A B C D(19)           18-13     85 Direct Blue 108  --  --  0.8 Water  20 15 A A A B C D(20)     22-7  86 Acid Blue 102/ 80/20 Orthosilicic 100/200 --  0.5 Water/ 95/5     15 " A A A A A A(0.2)  Basic Orange 14  acid     Isobutyl  17-12     alcohol 87 Solvent Black 5  Colloidal silica 100/150 Shellac resin     100/50 1.0 Methanol  14 " A A A A A A(0.3)           16-11 88 Solvent     Black 5  --  --  0.5 Methanol  12 " A A A A A A(0.5)           14-9  89     Basic Red 2  Fe(OH).sub.3 sol 100/50  --  0.8 Methanol  15 " A A A A A     A(0.9)           17-13 90 Solvent Black 7  FeCl.sub.2 100/5  --  0.5     Methanol  14 " A A A A A A(0.7)           16-10     Notes:     (1) *comparative examples     (2) Dye or pigment concentration in coating solution.     (3) Chloride ion concentration in slurry after completion of     polymerization     (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h

EXAMPLE 2

As shown in Table 2, for each experiment, a dye or a pigment wasdissolved or dispersed in a solvent, optionally with the addition of aninorganic compound or a polymeric compound as shown in the same Table toprepare a coating solution. The formulation ratio of the inorganiccompound and the polymeric compound and the concentration of dye orpigment in the coating solution are also shown in Table 2. The coatingsolution was applied on the polished inner wall surface of a stainlesssteel polymerizer of an inner volume of 1000 liters and the portionswhich may contact with monomers such as stirrer, dried at 70° C. for 20minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 200 Kg of vinylchloride monomer, 400 Kg of deionized water, 2.2 Kg of sodium laurylsulfate, 3.2 Kg of cetyl alcohol and 300 g ofα,α'-azobis-2,4-dimethylvaleronitrile, and polymerization was carriedout at 50° C. for 10 hours. After completion of polymerization, thepolymer was taken out and the polymerizer was washed internally withwater at a flow rate of 0.1 m³ /m² hr, as shown in Table 2. The aboveoperations from coating and charging to washing with water wereconducted for each batch and this was repeated for a maximum of 200batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. The conditions and theresults are shown in Table 2.

In Table 2, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 91 and 92 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound. Also, the coating solutionemployed in Experiment Nos. 104 and 149 was prepared by dissolving onepart of sodium sulfide in 100 parts of water and adding 0.5 part of adye to the resultant solution, followed by heating at 80° C. for 30minutes.

                                      TABLE 2                                     __________________________________________________________________________    Coating Solution                                                              (1)                                                                              Dye or pigment (a)                                                                            Inorganic  (a)/(b)                                                                            Polymeric  (a)/(c)                                                                            (2)                                                                              Solvent                 Exp.           Mixing                                                                            compound   weight                                                                             compound   weight                                                                             conc.   Mixing             No.                                                                              Kind        ratio                                                                             (b)        ratio                                                                              (c)        ratio                                                                              %  Kind ratio              __________________________________________________________________________     91*                                                                             --              --              --                 --                       92*                                                                             --              --              --                 --                       93*                                                                             Acid Green 16   --              --              0.5                                                                              Water/                                                                             90/10                                                                    Isobutyl                                                                      alcohol                  94*                                                                             "               12-Silicotungstic                                                                        100/150                                                                            --              0.5                                                                              Water                                      acid                                                        95*                                                                             Acid Green 40   Colloidal silica                                                                         100/100                                                                            --              1.0                                                                              Methanol                 96*                                                                             --              "           0/100                                                                             --              1.0                                                                              Water                    97*                                                                             Acid Black 2    Silicomolybdic acid                                                                      100/100                                                                            --              1.0                                                                              "                        98*                                                                             Solvent Black 5 --              --              0.5                                                                              Methanol                 99*                                                                             "               CuCl.sub. 2                                                                              100/10                                                                             --              0.5                                                                              "                       100*                                                                             Basic 47        Water glass                                                                              100/200                                                                            --              0.8                                                                              Water                   101*                                                                             Pigment Blue 25/                                                                          50/50                                                                             Colloidal silica                                                                         100/400                                                                            --              2.0                                                                              Water/                                                                             10/90                 Solvent Black 3                                    Methanol                102*                                                                             Solvent Red 8   --              --              0.5                                                                              Methanol                103*                                                                             Pigment Red 81  --              Polystyrene                                                                              100/40                                                                             1.2                                                                              Toluene                 104*                                                                             Sulfur Brown 7  Colloidal silica                                                                         100/60               1.0                                                                              Water                   105                                                                              Disperse Red 12 --              --              0.5                                                                              Acetone                 106                                                                              Acid Red 8      --              --              0.8                                                                              Water                   107                                                                              Basic Blue 64   --              --              0.7                                                                              "                       108                                                                              Pigment Blue 25/                                                                          50/50                                                                             Colloidal silica                                                                         100/400                                                                            --              1.8                                                                              Water/                                                                             10/90                 Solvent Black 3                                    Methanol                109                                                                              Mordant Green 15                                                                              --              --              0.4                                                                              Water                   110                                                                              Solvent Red 8   --              --              0.5                                                                              Methanol                111                                                                              Solvent Red 8   Colloid of vanadium                                                                      100/3                                                                              --              0.5                                                                              "                                          pentoxide                                                  112                                                                              Acid Yellow 99  --              --              0.3                                                                              Water                   113                                                                              Solvent Orange 40                                                                             --              Poly(4-vinylpyridine)                                                                     100/100                                                                           1.0                                                                              Methanol                114                                                                              Basic Blue 47   Water glass                                                                              100/200                                                                            --              0.8                                                                              Water                   115                                                                              Vat Black 25/Disperse                                                                     60/40                                                                             --              Poly(N--vinyl-                                                                           100/70                                                                             0.7                                                                              Methanol                   Violet 30                       carbazole                                  116                                                                              Solvent Blue 35 Mesosilicic acid                                                                         100/20               0.5                                                                              "                       117                                                                              Direct Red 9    --              --              0.8                                                                              Water/n-                                                                           80/20                                                                    Butyl                                                                         alcohol                 118                                                                              Acid Green 40   Colloidal silica                                                                         100/100                                                                            --              1.0                                                                              Water/                                                                             40/60                                                                    Methanol                119                                                                              Acid Red 82     --              --              1.0                                                                              Water/                                                                             50/50                                                                    Methanol                120                                                                              Solvent Black 5 CuCl.sub.2 100/10                                                                             --              0.6                                                                              Water/                                                                             30/70                                                                    Methanol                121                                                                              Solvent Black 5 --              --              0.4                                                                              Methanol                122                                                                              Vat Blue 41     --              --              0.4                                                                              Xylene                  123                                                                              Solubilized Vat Black 1                                                                       Mesodisilicic acid                                                                       100/300                                                                            --              0.7                                                                              Water                   124                                                                              Vat Violet 3    --              --              0.5                                                                              Xylene                  125                                                                              Pigment Green 37                                                                              --              Polyvinylmethylether                                                                     100/40                                                                             1.0                                                                              Methylene                                                                     chloride                126                                                                              Mordant Green 58                                                                              --              --              1.2                                                                              Water                   127                                                                              Solvent Black 7 Mesotetrasilicic acid                                                                    100/100                                                                            --              1.0                                                                              Methylene                                                                     chloride                128                                                                              Basic Orange 2  Metasilicic acid                                                                         100/40                                                                             --              0.8                                                                              Water                   129                                                                              Basic Yellow 2  --              --              0.4                                                                              "                       130                                                                              Basic Blue 40   --              --              0.6                                                                              "                       131                                                                              Acid Green 16   12-Silicotungstic                                                                        100/150                                                                            --              0.5                                                                              "                                          acid                                                       132                                                                              Basic Orange 14 --              --              1.0                                                                              Water/                                                                        Isobutyl                                                                      alcohol                 133                                                                              Basic Orange 14 MgCl.sub.2 100/10                                                                             --              1.0                                                                              Water/                                                                             90/10                                                                    Isobutyl                                                                      alcohol                 134                                                                              Pigment Red 81  --              Polystyrene                                                                              100/50                                                                             1.2                                                                              Toluene                 135                                                                              Acid Red 87     --              --              0.8                                                                              Water                   136                                                                              Acid Blue 59/                                                                             30/70                                                                             --              --              0.8                                                                              Water/                                                                             40/60                 Solvent Blue 73                                    Methanol                137                                                                              Acid Black 2    Silicomolybdic acid                                                                      100/100                                                                            --              1.0                                                                              Water                   138                                                                              Basic Blue 3    --              --              2.0                                                                              "                       139                                                                              Direct Blue 106 --              --              0.4                                                                              Water                   140                                                                              Acid Yellow 3   Sodium orthosilicate                                                                     100/20                                                                             --              1.2                                                                              "                       141                                                                              Basic Blue 24   --              --              0.8                                                                              "                       142                                                                              Basic Red 27    Water glass                                                                              100/200                                                                            --              0.3                                                                              "                       143                                                                              Disperse Yellow 54                                                                            --              Polystyrene                                                                              100/30                                                                             0.6                                                                              Toluene                 144                                                                              Acid Yellow 1   --              --              0.8                                                                              Water/                                                                             70/30                                                                    Isoamyl                                                                       alcohol                 145                                                                              Acid Yellow 1   Zn (CH.sub.3 --COO).sub.2                                                                100/5                                                                              --              0.8                                                                              Water                   146                                                                              Disperse Blue 58                                                                              --              --              0.5                                                                              Acetone                 147                                                                              Pigment Red 123 --              Poly(1-nitropropylene)                                                                   100/50                                                                             1.0                                                                              DMF                     148                                                                              Vat Orange 15   --              --              0.8                                                                              Xylene                  149                                                                              Sulfur Red 3    --              --              1.0                                                                              Water                   150                                                                              Solubilized Sulfur                                                                            --              --              0.7                                                                              "                          Blue 15                                                                    151                                                                              Sulfur Brown 7  Colloidal silica                                                                         100/60                                                                             --              2.0                                                                              Water                   152                                                                              Fluorescent Brightening                                                                       --              --              0.8                                                                              "                          Agent 163                                                                  153                                                                              Fluorescent Brightening                                                                       --              --              0.8                                                                              "                          Agent 90                                                                   154                                                                              Azoic Black 1   Metasilicic acid                                                                         100/50                                                                             --              1.0                                                                              "                       155                                                                              Reactive Blue 8 --              --              0.6                                                                              "                       156                                                                              Reactive Black 18                                                                             --              --              0.6                                                                              Water/                                                                             80/20                                                                    Isobutyl                                                                      alcohol                 157                                                                              Reactive Black 18                                                                             Colloid of manganese                                                                     100/2                                                                              --              0.6                                                                              Water                                      dioxide                                                    __________________________________________________________________________                     (3)      (4)                                                                  Cl.sup.- Time for washing                                                                        Scaling                                                 (1)                                                                              upper: average                                                                         with water after                                                                        Visual evaluation (Amount attached                                            g/m.sup.2)                                              Exp.                                                                             lower: max.-min.                                                                       completion                                                                              Batch No.                                               No.                                                                              ppm      min.      10   30   50   100  150                                                                              200                __________________________________________________________________________                   91*                                                                             300      60        H(1400)                                                    260-320                                                                     92*                                                                             13       "         H(1200)                                                     8-17                                                                       93*                                                                             290      "         G    H(1100)                                               260-310                                                                     94*                                                                             300      "         B    C    F    H(900)                                      260-320                                                                     95*                                                                             350      "         B    C    F    H(800)                                      310-390                                                                     96*                                                                             15       "         H(1200)                                                    11-19                                                                       97*                                                                             280      "         B    C    F    H(700)                                      260-290                                                                     98*                                                                             300      "         B    F    H(1000)                                          260-320                                                                     99*                                                                             300      "         B    C    F    H(950)                                      260-320                                                                    100*                                                                             270      "         B    C    F    H(750)                                      240-280                                                                    101*                                                                             320      "         B    C    F    H(650)                                      270-350                                                                    102*                                                                             300      "         B    F    H(1000)                                          270-320                                                                    103*                                                                             250      "         B    F    H(900)                                           220-280                                                                    104*                                                                             300      "         B    F    H(950)                                           270-320                                                                    105                                                                              13       10        A    A    A    B    C  D(20)                                9-18                                                                      106                                                                              15       "         A    A    A    B    C  D(19)                               11-20                                                                      107                                                                              14       "         A    A    B    C    D  F(58)                                9-18                                                                      108                                                                              17       "         A    A    A    A    A  B(3)                                13-21                                                                      109                                                                              10       "         A    A    A    B    C  D(18)                                6-14                                                                      110                                                                              15       "         A    A    A    B    C  D(20)                               11-19                                                                      111                                                                              10       "         A    A    A    A    A  B(3)                                 8-13                                                                      112                                                                               5       "         A    A    B    C    D  F(60)                               3-7                                                                        113                                                                               9       "         A    A    A    A    B  C(10)                                5-13                                                                      114                                                                              16       15        A    A    A    A    A  B(3)                                13-18                                                                      115                                                                               8       "         A    A    A    B    C  D(20)                                6-11                                                                      116                                                                              15       "         A    A    A    A    A  B(1.5)                              10-18                                                                      117                                                                               9       "         A    A    A    B    C  D(20)                                5-12                                                                      118                                                                              16       "         A    A    A    A    A  B(2.5)                              13-19                                                                      119                                                                               8       "         A    A    B    C    D  F(59)                                5-10                                                                      120                                                                               7       "         A    A    A    A    A  B(3)                                5-9                                                                        121                                                                              20       "         A    A    A    A    B  C(5)                                15-23                                                                      122                                                                              11       10        A    A    B    C    D  F(55)                                8-14                                                                      123                                                                               7       "         A    A    A    A    A  B(1.5)                              6-8                                                                        124                                                                              15       "         A    A    A    B    C  D(18)                               11-17                                                                      125                                                                              16       "         A    A    A    B    C  D(19)                               11-18                                                                      126                                                                              10       "         A    A    A    B    C  D(20)                                5-12                                                                      127                                                                              14       "         A    A    A    A    A  B(3)                                10-18                                                                      128                                                                              18       15        A    A    A    A    A  B(4)                                15-21                                                                      129                                                                              11       "         A    A    A    B    C  D(18)                                9-14                                                                      130                                                                              17       "         A    A    A    B    C  D(17)                               15-19                                                                      131                                                                              10       "         A    A    A    A    A  B(3)                                 8-13                                                                      132                                                                              14       "         A    A    B    C    D  F(60)                               11-16                                                                      133                                                                              11       -         A    A    A    A    A  B(2.5)                               9-13                                                                      134                                                                              12       "         A    A    B    C    D  F(59)                                9-14                                                                      135                                                                               9       "         A    A    B    C    D  F(57)                                7-11                                                                      136                                                                              12       "         A    A    A    A    B  C(6)                                10-14                                                                      137                                                                              11       "         A    A    A    A    A  B(3)                                 9-14                                                                      138                                                                              19       "         A    A    B    C    D  F(60)                               15-23                                                                      139                                                                              13       "         A    A    B    C    D  F(60)                               10-15                                                                      140                                                                              10       "         A    A    A    A    A  B(3)                                 8-12                                                                      141                                                                               9       "         A    A    B    C    D  F(56)                                6-11                                                                      142                                                                              14       "         A    A    A    A    A  B(2.5)                              10-18                                                                      143                                                                              17       "         A    A    A    B    C  D(20)                               15-19                                                                      144                                                                              12       "         A    A    B    C    D  F(59)                                9-14                                                                      145                                                                              12       10        A    A    A    A    A  B(2.0)                               9-14                                                                      146                                                                              10       15        A    A    B    C    D  F(57)                                8-12                                                                      147                                                                              13       "         A    A    A    B    C  D(19)                               10-15                                                                      148                                                                               9       10        A    A    B    C    D  F(57)                                5-11                                                                      149                                                                              20       "         A    A    A    B    C  D(18)                               15-23                                                                      150                                                                              17       "         A    A    B    C    D  F(53)                               15-19                                                                      151                                                                              16       "         A    A    A    A    A  B(2.5)                              14-19                                                                      152                                                                              11       "         A    A    A    B    C  D(15)                                8-14                                                                      153                                                                               6       "         A    A    B    C    D  F(54)                               3-8                                                                        154                                                                              13       "         A    A    A    A    A  B(3)                                10-15                                                                      155                                                                              10       "         A    A    A    B    C  D(16)                                9-11                                                                      156                                                                              15       "         A    A    A    B    C  D(20)                               12-17                                                                      157                                                                              14       "         A    A    A    A    A  B(3)                                11-17                                                        __________________________________________________________________________     Notes:                                                                         (1) *comparative examples                                                     (2) Dye or pigment concentration in coating solution.                         (3) Chloride ion concentration in slurry after completion of                 polymerization                                                                 (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h                           

EXAMPLE 3

As shown in Table 3, for each experiment, a dye or a pigment wasdissolved or dispersed in a solvent, optionally with the addition of aninorganic compound or a polymeric compound as shown in the same Table toprepare a coating solution. The formulation ratio of the inorganiccompound and the polymeric compound and the concentration of the dye orpigment in the coating solution are also shown in Table 3. The coatingsolution was applied on the polished inner wall surface of a stainlesssteel polymerizer of an inner volume of 1000 liters and the portionswhich may contact with monomers such as stirrer, dried at 70° C. for 20minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 160 Kg of vinylchloride monomer, 40 Kg of vinyl acetate monomer, 400 Kg of deionizedwater, 600 g of gelatin, 2Kg of Triclene and 350 g of lauroyl peroxide,and polymerization was carried out at 70° C. for 6 hours. Aftercompletion of polymerization, the polymer was taken out and thepolymerizer was washed internally with water at a flow rate of 0.1 m³/m² hr, as shown in Table 3. The operations from coating and charging towashing with water were conducted for each batch and this was repeatedfor a maximum of 200 batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. The conditions and theresults are shown in Table 3.

In Table 3, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 158 and 159 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound. Also, the coating solutionemployed in Experiment No. 195 was prepared by dissolving one part ofsodium sulfide in 100 parts of water and adding 0.5 part of a dye to theresultant solution, followed by heating at 80° C. for 30 minutes.

    TABLE 3       (3) (4)  Coating Solution Cl.sup.-  conc. Time for washing Scaling (1) D     ye or pigment (a) Inorganic (a)/(b) Polymeric (a)/(c) (2) Solvent upper:     average with water after Visual evaluation (Amount attached g/m.sup.2)     Exp. Mixing compound weight compound weight conc.  Mixing lower:     max.-min. completion Batch No. No. Kind ratio (b) ratio (c) ratio % Kind r     atio ppm min. 10 30 50 100 150 200       158* --  --  --   --  350  60 H(1100)                390-320 159* --     --  --   --  10 " H(1000)           12-7  160* Solvent Black 7  --  --     0.5 Methanol  300  " B F H(500)           350-280 161* "  --  Polytetra-     100/30 0.6 THF  280  " B F H(300)      hydrofuran     330-260 162* Basic     Orange 2  Colloidal silica 100/100 --  1.0 Water  290  " B C F H       350-270 163* Solvent Black 5  --  Shellac resin 100/50 0.8 Methanol     250  " B F H(400)           280-230 164* "  Fe(OH).sub.3 sol 100/10  --     1.0 "  290  " B C F H(300)           340-270 165* Acid Black 2  Water     glass 100/100 --  1.5 Water/ 50/50 260  " B C F H(250)         Methanol     300-240 166* Basic Orange 14  Metasilicic acid  --  1.5 Methanol  250  "     B C F H(280)           300-220 167* --  Colloidal silica  0/100 --  1.0     Water  280  " H(900)           340-260 168* Solvent Blue 2  --  --  0.5     Methanol  270  " B F H(400)           320-250 169* Vat Violet 2  --  --     0.5 Xylene  290  " B F H(500)           340-270 170 Solvent Black 7  --     Polytetra- 100/30 0.6 THF  17 10 A A A A A A(0.3)      hydrofuran     19-14 171 Solvent Black 7  --  --  0.5 Methanol  16 " A A A A A A(0.5)             18-13 172 Pigment Red 17  --  Polyphenyl-  0.8 "  10 " A A A A B     C(10)      acetylene     12-7  173 Direct Blue 86  Orthosilicic acid     100/20  --  0.8 Water  16 " A A A A A A(0.7)           18-12 174 Basic     Orange 2  Colloidal silica 100/100 --  1.0 Water/n- 90/10 11 " A A A A A     A(0.5)         Butyl  13-7          alcohol 175 Direct Black 74  --  --     0.5 Water   9 15 A A A B C D(20)           11-6  176 Solvent Red 121  --      --  0.6 Methanol  13 " A A A B C D(19)           15-10 177 "  Colloid     of lithium 100/100 --  0.6 "  17 " A A A A A A(0.9)    silicate     20-15 178 Solvent Black 5  --  Shellac resin 100/50 0.8 "  18 " A A A A     A A(0.6)           20-15 179 Vat Black 8  --  --  0.6 Acetone  12 " A A     A B C D(17)           14-9  180 Mordant Black 13  Metasilicic acid     100/200 --  0.7 Water   9 " A A A A A A(0.9)           11-5  181 Solvent     Blue 36  --  --  0.4 Methanol   6 " A A A A B C(10)           8-3 182     Acid Red 80/ 80/20 --  --  0.8 Water/ 50/50 13 10 A A A A A B(3)  Basic     Orange 2       Methanol  15-10 183 Solvent Black 5  Fe(OH).sub.3 sol     100/10  --  1.0 Water/ 40/60 11 " A A A A A A(0.5)         Methanol     13-6  184 Reduced Vat Blue 1  --  --  0.6 Water  18 " A A A B C D(19)            20-15 185 Vat Violet 2  --  --  0.4 Xylene  14 " A A A B C D(19)              19-14 186 Mordant Green 29  --  --  0.3 Water  19 " A A A B C     D(18)           21-16 187 Solvent Blue 2  --  --  0.7 Methanol  20 15 A     A A B C D(17)           22-17 188 "  CoCl.sub.2 100/1  --  0.7 "  20 10     A A A A A A(0.5)           22-18 189 Food Red 14  --  --  0.8 Water  12     15 A A A B C D(16)           14-9  190 "  AlCl.sub.3 100/1  --  0.8 "     12 10 A A A A A A(0.5)           14-9  191 Acid Black 2  Water glass     100/100 --  1.5 Water/   5 15 A A A A A A(0.7)         Isobutyl  7-3         alcohol 192 Solvent Yellow 33  --  --  0.8 Water  16 " A A A B C     D(15)           18-13 193 Basic Orange 14  Metasilicic acid 100/500 --     1.5 Water/  11 15 A A A A A A(0.9)         sec-Butyl  13-8     alcohol 194 Acid Brown 161  --  --  0.6 Water  17 " A A A B C D(20)          19-14 195 Sulfur Blue 9  --  --  0.7 "  14 " A A A A B C(10)        16-11 196 Fluorescent  --  --  0.4 "      8 " A A A B C D(19)  Brightening Agent 14         10-5  197 Reactive     Green 8  --  --  0.5 "  16 " A A A B C D(15)           18-12 198 Azoic     Yellow 2  --  --  0.5 Methanol   9 " A A A B C D(16)           11-6  199     "  CoCl.sub.2 100/3  --  0.5 "  13 10 A A A A A A(0.7)     Notes:     (1) *comparative examples     (2) Dye or pigment concentration in coating solution.     (3) Chloride ion concentration in slurry after completion of     polymerization     (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h

EXAMPLE 4

As shown in Table 4, for each experiment, a dye or a pigment wasdissolved or dispersed in a solvent, optionally with the addition of aninorganic compound or a polymeric compound as shown in the same Table toprepare a coating solution. The formulation ratio of the inorganiccompound or the polymeric compound and the concentration of the dye orpigment in the coating solution are also shown in Table 4. The coatingsolution was applied on the polished inner wall surface of a stainlesssteel polymerizer of an inner volume of 1000 liters and the portionswhich may contact with monomers such as stirrer, dried at 80° C. for 10minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 200 Kg of vinylchloride monomer, 400 Kg of deionized water, 40 g of a partiallysaponified polyvinyl alcohol, 60 g of hydroxypropylmethyl cellulose and80 g of di-2-ethylhexylperoxycarbonate, and polymerization was carriedout at 57° C. for 7 hours. After completion of polymerization, thepolymer was taken out and the polymerizer was washed internally withwater at a flow rate of 0.1 m³ /m² hr, as shown in Table 4. The aboveoperations from coating and charging to washing with water wereconducted for each batch and this was repeated for a maximum of 200batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. Also, the numbers of fisheyes in the products obtained from the polymers produced in the 10th,30th, 50th, 100th, 150th and 200th batches in each experiment weremeasured as follows. A mixture of 100 parts by weight of a polymerobtained by dehydrating and drying the slurry after polymerization, 50parts by weight of DOP, 1 part by weight of dibutyltin laurate, 1 partby weight of cetyl alcohol, 0.25 part by weight of titanium oxide and0.05 part by weight of carbon black was kneaded between two rolls at150° C. for 7 minutes and then formed into a sheet with a thickness of0.2 mm. The number of fish eyes per 100 cm² contained in the sheet wasexamined according to the light transmission method. The conditions andthe results are shown in Table 4.

In Table 4, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 185 and 186 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound.

                                      TABLE 4                                     __________________________________________________________________________                  1                                                               Coating Solution                                                              (1)                                                                              Dye or pigment (a)                                                                             Inorganic                                                                              (a)/(b)                                                                            Polymeric                                                                              (a)/(c)                                                                             (2) Solvent                  Exp.           Mixing                                                                             compound weight                                                                             compound weight                                                                              conc.     Mixing             No.                                                                              Kind        ratio                                                                              (b)      ratio                                                                              (c)      ratio %   Kind  ratio              __________________________________________________________________________    200*                                                                             --               --            --                 --                       201*                                                                             --               --            --                 --                       202*                                                                             Solvent Black 7  --            --             0.5 Methanol                 203*                                                                             "                Fe(OH).sub.2 sol                                                                       100/20                                                                             --             0.5 Water/                                                                              10/90                                                                   Methanol                 204*                                                                             Basic Orange 2/Solvent                                                                    60/40                                                                              --            --             0.8 Water/                                                                              50/50                 Black 3                                           Methanol                 205*                                                                             Solvent Black 5  Colloidal silica                                                                       100/80                                                                             --             0.8 Methanol                 206*                                                                             Acid Black 2     Metasilicic acid                                                                       100/50                                                                             --             0.8 Water                    207                                                                              Solvent Black 7  Fe(O)H.sub.3 sol                                                                       100/20                                                                             --             0.5 Water/                                                                              10/90                                                                   Methanol                 208                                                                              Basic Orange 2/Solvent                                                                    60/40                                                                              --            --             0.8 Water/                                                                              50/50                 Black 3                                           Methanol                 209                                                                              Solubilized Sulfur                                                                             --            --             0.8 Water                       Brown 1                                                                    210                                                                              Solvent Black 5  Colloidal silica                                                                       100/80                                                                             --             0.8 Methanol                 211                                                                              Azoic Black 5                  Shellac resin                                                                          100/100                                                                             1.0 "                        212                                                                              Pigment Green 38 --            Ethylcellulose                                                                         100/40                                                                              1.4 Ethanol                  213                                                                              Solvent Black 5  --            --             0.5 Methanol                 214                                                                              Basic Orange 14  --            --             0.9 Water/                                                                              90/10                                                                   Isobutyl                                                                      alcohol                  215                                                                              Solvent Black 23 --            --             0.8 Methanol                 216                                                                              Solvent Blue 73  --            --             0.4 "                        217                                                                              Acid Black 2     Metasilicic acid                                                                       100/50                                                                             --             0.8 Water                    __________________________________________________________________________       (3)      (4)                                                                  Cl.sup.- Time for washing                                                                       Scaling                                                  (1)                                                                              upper: average                                                                         with water after                                                                       Visual evaluation (Amount attached                                                                   Fish eyes (number)                Exp.                                                                             lower: max.-min.                                                                       completion                                                                             Batch No.              Batch No.                         No.                                                                              ppm      min.     10   30 50  100 150                                                                              200 10 30  50 100                                                                              150                                                                              200               __________________________________________________________________________    200*                                                                             300      60       H(1000)                300                                  260-300                                                                    201*                                                                             10       "        H(950)                 280                                   8-12                                                                      202*                                                                             290      "        B    F  H(700)         10 180 250                           250-310                                                                    203*                                                                             300      "        B    C  F   H(500)     13 50  60 100                        260-330                                                                    204*                                                                             280      "        B    F  H(650)         11 120 190                           240-300                                                                    205*                                                                             250      "        B    C  F   H(500)     18 40  80 120                        200-270                                                                    206*                                                                             260      "        B    C  F   H(560)     15 50  100                                                                              150                        210-290                                                                    207                                                                              14       15       A    A  A   A   A  A(0.5)                                                                            0  0   0  0  2  10                   10-16                                                                      208                                                                              10       "        A    A  A   A   A  A(0.7)                                                                            0  0   0  0  3  15                    8-12                                                                      209                                                                              12       "        A    A  A   A   B  C(10)                                                                             0  0   0  2  7  20                    9-14                                                                      210                                                                               8       "        A    A  A   A   A  A(0.2)                                                                            0  0   0  0  1  5                     6-10                                                                      211                                                                              13       "        A    A  A   A   B  C(9)                                                                              0  0   0  1  10 25                   15-10                                                                      212                                                                              18       "        A    A  A   A   B  C(12)                                                                             0  0   0  4  10 19                   20-15                                                                      213                                                                               7       15       A    A  A   A   A  A(0.6)                                                                            0  0   0  0  5  11                   4-9                                                                        214                                                                              10       "        A    A  A   A   B  C(9)                                                                              0  0   0  3  11 27                    7-12                                                                      215                                                                              11       "        A    A  A   A   A  B(3)                                                                              0  0   0  0  5  15                    8-13                                                                      216                                                                              20       "        A    A  A   A   B  C(10)                                                                             0  0   0  7  15 35                   18-22                                                                      217                                                                              13       "        A    A  A   A   A  A(0.3)                                                                            0  0   0  0  2  10                   10-15                                                                      __________________________________________________________________________     (1) *comparative examples                                                     (2) Dye or pigment concentration in coating solution.                         (3) Chloride ion concentration in slurry after completion of                  polymerization                                                                (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h                            

EXAMPLE 5

As shown in Table 5, for each experiment, a conjugated π compound wasdissolved or dispersed in a solvent, optionally with the addition of aninorganic compound or a polymeric compound as shown in the same Table toprepare a coating solution. The formulation ratio of the inorganiccompound or the polymeric compound and the concentration of theconjugated π bond compound in the coating solution are also shown inTable 5. The coating solution was applied on the polished inner wallsurface of a stainless steel polymerizer of an inner volume of 1000liters and the portions which may contact with monomers such as stirrer,dried at 70° C. for 20 minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 200 Kg of vinylchloride monomer, 400 Kg of deionized water, 44 g of a partiallysaponified polyvinyl alcohol, 56 g of hydroxypropylmethyl cellulose and60 g of t-butylperoxyneodecanate, and polymerization was carried out at52° C. for 7 hours. After completion of polymerization, the polymer wastaken out and the polymerizer was washed internally with water at a flowrate of 0.1 m³ /m² hr, as shown in Table 5. The above operations fromcoating and charging to washing with water were conducted for each batchand this was repeated for a maximum of 200 batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. The conditions and theresults are shown in Table 5.

In Table 5, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 301 and 302 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound. Also, the coating solutionemployed in Experiment Nos. 333 and 334 was prepared by dissolving onepart of sodium sulfide in 100 parts of water and adding 0.5 part of adye to the resultant solution, followed by heating at 80° C. for 30minutes.

                                      TABLE 5                                     __________________________________________________________________________    Coating Solution                                                              (1)                                                                              Conjugated π bond compound (a)                                                               Inorganic                                                                             (a)/(b)                                                                            Polymeric  (a)/(c)                                                                            (2)                                                                              Solvent                  Exp.            Mixing                                                                             compound                                                                              weight                                                                             compound   weight                                                                             conc.    Mixing             No.                                                                              Kind         ratio                                                                              (b)     ratio                                                                              (c)        ratio                                                                              %  Kind  ratio              __________________________________________________________________________     301*                                                                            --                --           --                 --                        302*                                                                            --                --           --                 --                        303*                                                                            Rosaniline        --           --              0.5                                                                              Methanol                  304*                                                                            "                 --           --              0.5                                                                              "                         305*                                                                            "                 --           --              0.5                                                                              "                         306*                                                                            "                 Colloidal silica                                                                      100/100                                                                            --              1.0                                                                              "                         307*                                                                            "                 "       100/200                                                                            Shellac resin                                                                            100/20                                                                             1.5                                                                              "                         308*                                                                            --                "        0/100                                                                             --              1.0                                                                              Water                     309*                                                                            Leucoquinizarin/                                                                           90/10                                                                              Fe(OH).sub.3 sol                                                                      100/50                                                                             --              0.7                                                                              Water/                                                                              20/80                 Solvent Black 7                                   Methanol                  310*                                                                            Flavonol          --           --              0.8                                                                              Methanol                  311*                                                                            Indigoazine       NiCl.sub.2                                                                            100/5                                                                              --              0.4                                                                              "                         312*                                                                            Acridone          --           --              0.5                                                                              "                         313*                                                                            2-Oxythiophanthrene                                                                             --           --              0.3                                                                              "                         314*                                                                            Phthalazine/ 50/50                                                                              --           --              0.5                                                                              "                           Acid Blue 59                                                                315*                                                                            --                --           Shellac resin                                                                              0/100                                                                            1.0                                                                              "                         316*                                                                            Carocyanine       --           --              0.7                                                                              "                        317                                                                              2,2-Diphenylolpropane                                                                           --           --              0.7                                                                              "                        318                                                                              Oxyanthraquinone/                                                                          50/50                                                                              --           --              0.9                                                                              "                           Solvent Black 5                                                            319                                                                              Rosaniline        Colloidal silica                                                                      100/100                                                                            --              0.6                                                                              Water/                                                                              20/80                                                                   Methanol                 320                                                                              Rosaniline/Quinoline                                                                            --           Shellac resin                                                                            100/20                                                                             0.7                                                                              Methanol                 321                                                                              4-Aminodiphenylamine                                                                            --           --              0.5                                                                              "                        322                                                                              2-Aminophenazine  --           --              0.8                                                                              "                        323                                                                              2-Aminodiphenylamine                                                                            --           --              0.4                                                                              "                        324                                                                              7-Amino-4-        --           --              0.7                                                                              "                           methylcoumarine                                                            325                                                                              Phenazineoxide/                                                                            40/60                                                                              Colloidal silica                                                                      100/200                                                                            --              0.5                                                                              Water/                                                                              40/60                 Acid Black 2                                      Methanol                 326                                                                              Malonic acid bis(β-                                                                        --           --              0.9                                                                              Methanol                    phenylhydrazine)                                                           327                                                                              3,4-Benzoquinoline                                                                              --           --              0.7                                                                              "                        328                                                                              Benzoflavin       --           --              0.3                                                                              "                        329                                                                              Triphenylisooxazole                                                                             --           --              0.9                                                                              "                        330                                                                              Nitrodiphenylether                                                                              --           --              0.4                                                                              "                        331                                                                              Picene-5,6-quinone                                                                              --           Polypyridylacetylene                                                                      100/100                                                                           1.0                                                                              "                        332                                                                              Indoaniline       --           --              0.4                                                                              "                        333                                                                              Hydron Blue/ 80/20                                                                              --           --              0.8                                                                              "                           Basic Black 2                                                              334                                                                              Benzo[a]benzofuran                                                                              --           --              0.5                                                                              "                        335                                                                              3,4-Phthaloylfurazane                                                                           --           --              0.5                                                                              "                        336                                                                              3-Cinnamyl-2-methyl-                                                                            --           --              0.9                                                                              "                           1,4-naphthoquinone                                                         337                                                                              Alizarine         --           --              0.4                                                                              "                        338                                                                              Leucoquinizarin/                                                                           90/10                                                                              Fe(OH).sub.3 sol                                                                      100/50                                                                             --              0.7                                                                              Water/                                                                              20/80                 Solvent Black 7                                   Methanol                 339                                                                              2,2'-Dianthraquinolyl                                                                           --           --              0.8                                                                              Methanol                 340                                                                              Anhydronium Base  --           --              0.2                                                                              "                        341                                                                              Chromonol/   20/80                                                                              --           --              0.5                                                                              "                           Basic Orange 14                                                            342                                                                              Flavonol          --           --              0.8                                                                              "                        343                                                                              Dicoumarol        --           --              1.0                                                                              "                        344                                                                              Isoxanthone       --           --              1.2                                                                              "                        345                                                                              1-Phenylpyrrole   --           --              0.8                                                                              "                        346                                                                              3-Phenylindole    --           Polyvinylisobutyral                                                                      100/20                                                                             1.0                                                                              Chloroform               347                                                                              Indigoazine       NiCl.sub.2                                                                            100/5                                                                              --              0.4                                                                              Methanol                 348                                                                              β-Isoindigo  --           --              0.6                                                                              "                        349                                                                              1,1'-Dicarbazole  --           --              0.5                                                                              "                        350                                                                              Porphyne/    20/80                                                                              --           Polysarcosine                                                                            100/50                                                                             0.8                                                                              "                           Solvent Black 5                                                            351                                                                              4-Phenylthiazole  --           --              0.4                                                                              "                        352                                                                              4-Phenylimidazole --           --              0.8                                                                              "                        353                                                                              5-Phenylpyrazole  --           --              0.9                                                                              "                        354                                                                              Phenylfuroxane    --           --              0.5                                                                              "                        355                                                                              2-Phenyl-1,3,4-thiadiazole                                                                      Metatetrasilicic                                                                      100/100                                                                            --              0.7                                                                              Water/                                                                              30/70                                   acid                            Methanol                 356                                                                              2-Phenyl-1,2,3-triazole                                                                         --           --              0.4                                                                              Methanol                 357                                                                              1-Oxy-5-phenyltetrazole                                                                         --           --              0.8                                                                              "                        358                                                                              4-Pyridyl-m-      --           Hydroxyethylcellulose                                                                     100/100                                                                           1.0                                                                              Acetone                     phenylenediamine                                                           359                                                                              Quinophthalone    --           --              0.3                                                                              Methanol                 360                                                                              5-Iodoisoquinoline                                                                              --           --              0.6                                                                              "                        361                                                                              9-Phenoxyacridine --           --              0.5                                                                              "                        362                                                                              3-Oxyphenanthridinone                                                                           --           --              0.4                                                                              "                        363                                                                              2-Benzoylcoumarone                                                                              --           --              0.8                                                                              "                        364                                                                              Hydrovanilloyl/                                                                            20/80                                                                              Fe(OH).sub.3 sol                                                                      100/5                                                                              --              0.5                                                                              "                           Solvent Black 5                                                            365                                                                              1,3-Dioxyacridine --           --              0.7                                                                              "                        366                                                                              o-Oxybenzophenone/                                                                         70/30                                                                              --           --              0.8                                                                              "                           Solvent Blue 73                                                            367                                                                              2,5-Dioxybenzophenone                                                                           --           --              0.7                                                                              "                        368                                                                              Acridone          --           --              0.5                                                                              "                        369                                                                              2-Oxy-3-phenylindazole                                                                          --           --              0.5                                                                              "                        370                                                                              Xanthene          --           --              0.6                                                                              "                        371                                                                              2,4-Dinitro-9-    --           --              0.8                                                                              "                           phenylacridine                                                             372                                                                              4,4'-Dibenzoylidiphenyl                                                                         --           --              0.4                                                                              "                        373                                                                              Diaminobenzophenone                                                                             --           Butylcellulose                                                                           100/20                                                                             0.8                                                                              Ethanol                  374                                                                              Tetramethoxyindigo/                                                                        60/40                                                                              Colloidal silica                                                                      100/200                                                                            --              0.8                                                                              Water/                                                                              40/60                 Phenoazoxide                                      Methanol                 375                                                                              Terphenyl/1,4-                                                                             50/50                                                                              --           --              0.6                                                                              Methanol                    diphenylnaphthalene                                                        376                                                                              Aminomethylnaphthalene                                                                          --           --              0.8                                                                              "                        377                                                                              1-Iodonaphthalene --           --              0.3                                                                              "                        378                                                                              3,4-Benzcarbazole --           --              0.5                                                                              "                        379                                                                              α-Naphthol  --           --              0.7                                                                              "                        380                                                                              Methylene-di-β-                                                                            --           --              0.4                                                                              "                           naphthol                                                                   381                                                                              2-Methoxynaphthalene                                                                            --           --              0.7                                                                              "                        382                                                                              α,β-Naphthophenyxazine                                                               --           --              0.8                                                                              "                        383                                                                              2,6-Naphthoquinone/                                                                        70/30                                                                              --           --              0.5                                                                              "                           Basic Red 2                                                                384                                                                              2-Naphthalene-2'- Colloidal silica                                                                      100/50                                                                             --              1.0                                                                              Water/                                                                              30/70                 indoleindigo                                      Methanol                 385                                                                              Naphthoanilide    --           --              0.3                                                                              Methanol                 386                                                                              α-Pyridonaphthalone/                                                                 10/90                                                                              --           --              0.5                                                                              "                           Solvent Black 3                                                            387                                                                              α-Nitroso-β-naphthol                                                                 Colloidal silica                                                                      100/100                                                                            --              0.8                                                                              Water/                                                                              40/60                                                                   Methanol                 388                                                                              2-Anilinoanthracene                                                                             --           --              1.0                                                                              Methanol                 389                                                                              2-Amino-1-anthranol                                                                             --           --              0.9                                                                              "                        390                                                                              Anthracene-9-aldehyde                                                                           --           --              0.5                                                                              "                        391                                                                              1-Aminophenanthrene                                                                             --           --              0.6                                                                              "                        392                                                                              Phenanthrene-1,2-quinone                                                                        --           --              0.8                                                                              "                        393                                                                              2-Iodophenanthrene                                                                              --           --              0.7                                                                              "                        394                                                                              2-Amino-3-        Colloidal silica                                                                      100/500                                                                            --              0.8                                                                              Water/                                                                              20/80                 oxyphenanthrenequinone                            Methanol                 395                                                                              2,7-Diphenyl[2,3-g]-                                                                            --           --              0.6                                                                              Methanol                    quinoline                                                                  396                                                                              1,10-Phenanthroline                                                                             Fe(OH).sub.3 sol                                                                      100/20                                                                             --              0.8                                                                              Water/                                                                              50/50                                                                   Methanol                 397                                                                              1,9-Pyridoindole  --           --              0.4                                                                              Methanol                 398                                                                              3-Amino-1,5-      --           Poly(N--vinyl-1,2,4-                                                                     100/30                                                                             1.0                                                                              DMF                         naphthyridine                  triazole)                                   399                                                                              Carocyanine       --           --              0.7                                                                              Methanol                 400                                                                              Phenothiazine     Colloidal silica                                                                      100/40                                                                             --              0.9                                                                              Water/                                                                              30/70                                                                   Methanol                 401                                                                              Phthalazine/ 50/50                                                                              --           --              0.5                                                                              Methanol                    Acid Blue 59                                                               402                                                                              1-Aminophenazine  --           --              0.4                                                                              "                        403                                                                              2,4,6-Triphenyl-S--                                                                             --           Poly(9-    100/50                                                                             0.6                                                                              Methylene                   triazine                       vinylanthracene)   chloride                 404                                                                              2-Phenylthiophene --           --              0.9                                                                              Methanol                 405                                                                              3-Oxythiophanthrene                                                                             --           --              0.3                                                                              "                        406                                                                              Thioflavone       --           --              0.4                                                                              "                        407                                                                              2-Aminophenoxanthine                                                                            --           --              0.5                                                                              "                        408                                                                              Tetrahydroberberine                                                                             --           --              0.8                                                                              "                        409                                                                              Nicotylene        --           --              0.5                                                                              "                        410                                                                              Azlene            --           --              0.7                                                                              "                        411                                                                              Rosarine          --           --              0.5                                                                              "                        412                                                                              "                 Colloidal silica                                                                      100/200                                                                            Shellac resin   1.5                                                                              "                        __________________________________________________________________________                         (3)      (4)                                                                  Cl.sup.- conc.                                                                         Time for washing                                                                        Scaling                                                 (1)                                                                              upper: average                                                                         with water after                                                                        Visual evaluation (Amount                                                     attached g/m.sup.2)                                     Exp.                                                                             lower: max.-min.                                                                       completion                                                                              Batch No.                                               No.                                                                              ppm      min.      10   30  50  100 150                                                                             200                __________________________________________________________________________                       301*                                                                            300      60         H(1000)                                                   280-350                                                                     302*                                                                            15       "         H(900)                                                     12-17                                                                       303*                                                                            300      "         B    F   H(850)                                            270-350                                                                     304*                                                                            210      "         B    F   H(600)                                            190-250                                                                     305*                                                                            140      "         B    F   H(500)                                            120-180                                                                     306*                                                                            290      "         B    C   F   H(400)                                        270-310                                                                     307*                                                                            240      "         B    C   F   H(350)                                        220-300                                                                     308*                                                                            11       "         H(900)                                                      9-13                                                                       309*                                                                            280      "         B    C   F   H(350)                                        260-330                                                                     310*                                                                            270      "         G    H(500)                                                250-320                                                                     311*                                                                            290      "         G    H(300)                                                270-350                                                                     312*                                                                            250      "         G    H(600)                                                230-290                                                                     313*                                                                            290      "         G    H(700)                                                270-340                                                                     314*                                                                            270      "         G    H(350)                                                250-320                                                                     315*                                                                            240      "         H(950)                                                     220-290                                                                     316*                                                                            220      "         G    H(550)                                                200-280                                                                    317                                                                              13       10        A    A   A   B   C D(20)                                   10-15                                                                      318                                                                              15       "         A    A   A   A   A A(0.7)                                  13-17                                                                      319                                                                               7       "         A    A   A   A   A B(1.5)                                  5-9                                                                        320                                                                               4       "         A    A   A   A   A B(3)                                    3-5                                                                        321                                                                              17       "         A    A   A   B   C D(17)                                   14-21                                                                      322                                                                              14       "         A    A   A   A   B C(9)                                    10-18                                                                      323                                                                              16       "         A    A   A   B   C D(20)                                   12-18                                                                      324                                                                              13       "         A    A   A   B   C D(22)                                   10-17                                                                      325                                                                              11       15        A    A   A   A   A A(0.2)                                   8-14                                                                      326                                                                               9       "         A    A   A   B   C D(18)                                    7-12                                                                      327                                                                              12       "         A    A   A   B   C D(20)                                    8-15                                                                      328                                                                              10       "         A    A   A   B   C D(15)                                    7-13                                                                      329                                                                              15       "         A    A   A   B   C D(17)                                   11-17                                                                      330                                                                              20       "         A    A   A   B   C D(21)                                   16-22                                                                      331                                                                              14       "         A    A   A   A   B C(10)                                   10-16                                                                      332                                                                               7       "         A    A   A   B   C D(20)                                   5-9                                                                        333                                                                              10       10        A    A   A   A   A B(1.3)                                   8-12                                                                      334                                                                               8       "         A    A   A   B   C D(18)                                    6-10                                                                      335                                                                              16       "         A    A   A   B   C D(20)                                   13-18                                                                      336                                                                              10       "         A    A   A   B   C D(24)                                    8-12                                                                      337                                                                              13       "         A    A   A   B   C D(21)                                   10-15                                                                      338                                                                              12       "         A    A   A   A   A A(0.5)                                   9-14                                                                      339                                                                               9       15        A    A   A   B   C D(20)                                    6-11                                                                      340                                                                              11       "         A    A   A   B   C D(18)                                    8-13                                                                      341                                                                              19       "         A    A   A   A   A B(1.4)                                  15-22                                                                      342                                                                              14       "         A    A   A   B   C D(18)                                   10-16                                                                      343                                                                              12       "         A    A   A   B   C D(19)                                    9-14                                                                      344                                                                               6       "         A    A   A   B   C D(20)                                   4-8                                                                        345                                                                              10       "         A    A   A   B   C D(16)                                    7-13                                                                      346                                                                              14       "         A    A   A   A   A B(3)                                    11-17                                                                      347                                                                              12       "         A    A   A   A   A B(1.2)                                   9-14                                                                      348                                                                              19       "         A    A   A   B   C D(17)                                   15-23                                                                      349                                                                               7       "         A    A   A   B   C D(20)                                    5-10                                                                      350                                                                               8       "         A    A   A   A   A A(0.5)                                   6-11                                                                      351                                                                              14       "         A    A   A   B   C D(18)                                   10-16                                                                      352                                                                              12       "         A    A   A   B   C D(17)                                    9-14                                                                      353                                                                              10       "         A    A   A   B   C D(15)                                    7-13                                                                      354                                                                              12       "         A    A   B   C   D F(55)                                    9-14                                                                      355                                                                              15       "         A    A   A   A   A B(2.1)                                  12-18                                                                      356                                                                               8       "         A    A   B   C   D F(53)                                    5-10                                                                      357                                                                              14       10        A    A   B   C   D F(56)                                   11-17                                                                      358                                                                               7       "         A    A   A   A   B C(10)                                   5-9                                                                        359                                                                              10       "         A    A   A   B   C D(17)                                    8-12                                                                      360                                                                              12       "         A    A   B   C   D F(56)                                   10-14                                                                      361                                                                              15       "         A    A   A   B   C D(15)                                   12-18                                                                      362                                                                              20       "         A    A   A   B   C D(17)                                   17-23                                                                      363                                                                              13       "         A    A   B   C   D F(54)                                   10-16                                                                      364                                                                              16       "         A    A   A   A   A A(0.5)                                  14-19                                                                      365                                                                              12       "         A    A   A   B   C D(18)                                    9-15                                                                      366                                                                               9       15        A    A   A   A   A B(2.3)                                   5-11                                                                      367                                                                              17       "         A    A   A   B   C D(15)                                   14-20                                                                      368                                                                              11       "         A    A   A   B   C D(13)                                    8-14                                                                      369                                                                              12       "         A    A   A   B   C D(16)                                    9-15                                                                      370                                                                               8       "         A    A   A   B   C D(17)                                   5-10                                                                       371                                                                               5       "         A    A   A   B   C D(20)                                   3-7                                                                        372                                                                              12       "         A    A   A   B   C D(16)                                    9-14                                                                      373                                                                               8       "         A    A   A   A   A B(1.8)                                   5-10                                                                      374                                                                              14       "         A    A   A   A   A A(0.6)                                  11-17                                                                      375                                                                              17       10        A    A   A   B   C D(17)                                   14-20                                                                      376                                                                              11       "         A    A   B   C   D F(58)                                    7-15                                                                      377                                                                              16       "         A    A   B   C   D F(57)                                   14-18                                                                      378                                                                              10       "         A    A   A   B   C D(15)                                    7-13                                                                      379                                                                              15       "         A    A   B   C   D F(53)                                   13-17                                                                      380                                                                               8       "         A    A   B   C   D F(52)                                    5-10                                                                      381                                                                              15       "         A    A   A   B   C D(20)                                   11-18                                                                      382                                                                              17       "         A    A   A   B   C D(18)                                   13-20                                                                      383                                                                              11       "         A    A   A   A   A B(1.9)                                   9-14                                                                      384                                                                              12       "         A    A   A   A   A B(2.3)                                  10-15                                                                      385                                                                              10       "         A    A   B   C   D F(53)                                    7-13                                                                      386                                                                              14       "         A    A   A   A   A B(2.5)                                  11-18                                                                      387                                                                              14       "         A    A   A   A   A A(0.4)                                  11-17                                                                      388                                                                              18       "         A    A   A   B   C D(19)                                   15-22                                                                      389                                                                               5       "         A    A   A   B   C D(20)                                   3-7                                                                        390                                                                              11       "         A    A   A   B   C D(22)                                    9-14                                                                      391                                                                               9       "         A    A   A   B   C D(18)                                    6-12                                                                      392                                                                              12       15        A    A   A   B   C D(20)                                   10-15                                                                      393                                                                               8       "         A    A   A   B   C D(21)                                    5-11                                                                      394                                                                              11       "         A    A   A   A   A B(2.7)                                   8-14                                                                      395                                                                              15       "         A    A   B   C   D F(52)                                   12-18                                                                      396                                                                              10       "         A    A   A   A   A B(1.5)                                   7-13                                                                      397                                                                              13       "         A    A   A   B   C D(17)                                   10-16                                                                      398                                                                              20       "         A    A   A   A   A B(1.9)                                  15-25                                                                      399                                                                              12       "         A    A   B   C   D F(55)                                   11-13                                                                      400                                                                              10       "         A    A   A   A   A A(0.7)                                   8-14                                                                      401                                                                               7       "         A    A   A   A   A B(1.8)                                  5-9                                                                        402                                                                              19       10        A    A   A   B   C D(18)                                   14-23                                                                      403                                                                              16       "         A    A   A   A   A B(2.3)                                  13-19                                                                      404                                                                              14       "         A    A   A   B   C D(20)                                   11-18                                                                      405                                                                              16       "         A    A   A   B   C D(17)                                   13-19                                                                      406                                                                              20       "         A    A   A   B   C D(16)                                   16-24                                                                      407                                                                               6       "         A    A   B   C   D F(53)                                   5-8                                                                        408                                                                               9       "         A    A   B   C   D F(55)                                    7-12                                                                      409                                                                              11       "         A    A   A   B   C D(18)                                    9-13                                                                      410                                                                              18       "         A    A   A   B   C D(18)                                   15-21                                                                      411                   A    A   A   B   C D(20)                                412                   A    A   A   A   A A(0.5)             __________________________________________________________________________     Notes:                                                                        (1) *comparative examples                                                     (2) Conjugated π bond compound concentration in coating solution.          (3) Chloride ion concentration in slurry after completion of                  polymerization                                                                (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h                            

EXAMPLE 6

As shown in Table 6, for each experiment, a conjugated π bond compoundwas dissolved or dispersed in a solvent, optionally with the addition ofan inorganic compound or a polymeric compound as shown in the same Tableto prepare a coating solution. The formulation ratio of the inorganiccompound or the polymeric compound and the concentration of theconjugated π bond compound in the coating solution are also shown inTable 6. The coating solution was applied on the polished inner wallsurface of a stainless steel polymerizer of an inner volume of 1000liters and the portions which may contact with monomers such as stirrer,dried at 70° C. for 20 minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 200 Kg of vinylchloride monomer, 400 Kg of deionized water, 0.25 Kg ofhydroxypropylmethyl cellulose, 0.25 Kg of sorbitane monolaurate and 50 gof α,α'-azobis-2,4-dimethylvalelonitrile, and polymerization was carriedout at 57° C. for 10 hours. After completion of polymerization, thepolymer was taken out and the polymerizer was washed internally withwater at a flow rate of 0.1 m³ /m² hr, as shown in Table 6. The aboveoperations from coating and charging to washing with water wereconducted for each batch and this was repeated for a maximum of 200batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. The conditions and theresults are shown in Table 6.

In Table 6, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 413 and 414 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound.

                                      TABLE 6                                     __________________________________________________________________________    Coating Solution                                                              (1)                                                                              Conjugated π bond compound (a)                                                               Inorganic                                                                             (a)/(b)                                                                            Polymeric   (a)/(c)                                                                            (2)                                                                              Solvent                 Exp.             Mixing                                                                            compound                                                                              weight                                                                             compound    weight                                                                             conc.   Mixing             No.                                                                              Kind          ratio                                                                             (b)     ratio                                                                              (c)         ratio                                                                              %  Kind ratio              __________________________________________________________________________    413*                                                                             --                --           --                  --                      414*                                                                             --                --           --                  --                      415*                                                                             1-Bromonaphthalene                                                                              --           --               0.5                                                                              Methanol                416*                                                                             1-Naphthalene-2'- Fe(OH).sub.3 sol                                                                      100/30                                                                             --               0.6                                                                              Water/                                                                             20/80                 indoleindigo                                       Methanol                417*                                                                             9,10-Diamino- 50/50                                                                             Colloidal silica                                                                      100/100                                                                            --               1.2                                                                              Water/                                                                             50/50                 phenanthrene/Phenothiazine                         Methanol                418*                                                                             Dioxyacridone     --           --               0.6                                                                              Methanol                419*                                                                             --                Colloidal silica                                                                       0/100                                                                             --               1.0                                                                              Water                   420*                                                                             7-Oxy-3,4-        --           Polytetrahydrofuran                                                                       100/50                                                                             0.7                                                                              Benzene                    benzocoumarine                                                             421*                                                                             --                --           "            0/100                                                                             0.5                                                                              "                       422*                                                                             Indophenine       --           --               0.6                                                                              Methanol                423*                                                                             Nitrophenothiazine                                                                              --           --               0.4                                                                              "                       424*                                                                             Dianthraquinoneimide                                                                            --           --               0.5                                                                              "                       425*                                                                             6-Phenylcoumarine/                                                                          20/80                                                                             Colloidal silica                                                                      100/80                                                                             --               0.6                                                                              Water/                                                                             30/70                 Solvent Black 5                                    Methanol                426                                                                              N--Naphthylethylene-                                                                            --           Polycyclopentaneoxide                                                                     100/30                                                                             0.8                                                                              Benzene                    diamine                                                                    427                                                                              1-Bromonaphthalene                                                                              --           --               0.5                                                                              Methanol                428                                                                              1,1'-Diamino-2,2'-                                                                              Colloidal silica                                                                      100/50                                                                             --               1.0                                                                              Water/                                                                             30/70                 binaphthyl                                         Methanol                429                                                                              Benzoindanone     --           --               0.6                                                                              Methanol                430                                                                              Oxybenzoacridine  --           --               0.7                                                                              "                       431                                                                              1-Naphthalene-2'- Fe(OH).sub.3 sol                                                                      100/30                                                                             --               0.6                                                                              Water/                                                                             20/80                 indoleindigo                                       Methanol                432                                                                              α-Naphthoamidoxime                                                                        --           --               0.5                                                                              Methanol                433                                                                              α-Naphthylglyoxal                                                                         --           --               0.5                                                                              "                       434                                                                              9-Mercaptoanthracene                                                                            --           --               0.7                                                                              "                       435                                                                              9,10-Diamino- 50/50                                                                             Colloidal silica                                                                      100/100                                                                            --               1.2                                                                              Water/                                                                             50/50                 phenanthrene/Phenothiazine                         Methanol                436                                                                              2-Aminophenanthrene-                                                                            --           Polybutadiene                                                                             100/10                                                                             0.5                                                                              Water/                                                                             70/30                 quinone                                            Methanol                437                                                                              Perylene/2,2'-                                                                              90/10                                                                             --           --               0.8                                                                              Methanol                   dioxyazobenzene                                                            438                                                                              1,2-Benzophenazine                                                                              --           --               0.4                                                                              "                       439                                                                              2-Iodo-1,4-       --           --               0.5                                                                              "                          naphthoquinone                                                             440                                                                              Dianthraquinoneimide                                                                            --           --               0.5                                                                              "                       441                                                                              Quinizarinequinone                                                                              Fe(OH).sub.3 sol                                                                      100/10                                                                             --               0.5                                                                              Water/                                                                             20/80                                                                    Methanol                442                                                                              Dioxyacridone     --           --               0.6                                                                              Methanol                443                                                                              3,6-Diaminoacridene                                                                             colloidal silica                                                                      100/300                                                                            --               0.8                                                                              Water/                                                                             40/60                                                                    Methanol                444                                                                              4'-Nitroso-2-nitro-                                                                             --           --               0.7                                                                              Methanol                   diphenylamine                                                              445                                                                              4,4'-Dinitro-     --           --               0.9                                                                              "                          diphenylamine                                                              446                                                                              Dinitrophenylindazole                                                                           --           --               0.5                                                                              "                       447                                                                              Aminobenzophenone Colloidal silica                                                                      100/100                                                                            --               1.0                                                                              Water/                                                                             50/50                                                                    Methanol                448                                                                              1,3,8-Trinitro-   --           --               0.5                                                                              Methanol                   phenoxazine                                                                449                                                                              2,2'-Dioxybiphenyl                                                                              --           --               0.5                                                                              Methanol                450                                                                              6-Phenylcoumarine/                                                                          20/80                                                                             Colloidal silica                                                                      100/80                                                                             --               0.6                                                                              Water/                                                                             30/70                 Solvent Black 5                                    Methanol                451                                                                              7-Oxy-3,4-        --           Polytetrahydrofuran                                                                       100/50                                                                             0.7                                                                              Benzene                    benzocoumarine                                                             452                                                                              2-Phenyl-3-       Colloidal silica                                                                      100/40                0.9                                                                              Water/                                                                             50/50                 phenylazoindole                                    Methanol                453                                                                              Indophenine       --           --               0.6                                                                              Methanol                454                                                                              Polyphyrajine     --           --               0.7                                                                              "                       455                                                                              4-Phenyloxazole   --           --               0.6                                                                              "                       456                                                                              5-Benzoyl-3,4-    --           --               0.4                                                                              "                          diphenylisooxazole                                                         457                                                                              2-Amino-4-        Colloidal silica                                                                      100/150                                                                            --               0.8                                                                              Water/                                                                             30/70                 phenylthiazole                                     Methanol                458                                                                              2-Phenylazoimidazole                                                                            --           --               0.5                                                                              Methanol                459                                                                              4-Pyridylazoresorcin                                                                            Colloidal silica                                                                      100/200                                                                            --               0.8                                                                              Water/                                                                             40/60                                                                    Methanol                460                                                                              2,3-Quinolinediol --           --               0.6                                                                              Methanol                461                                                                              1-Aminoisoquinoline                                                                             --           --               0.7                                                                              Methanol                462                                                                              9-Oxyacridine/                                                                              70/30            Polyquinoxaline                                                                           100/60                                                                             1.0                                                                              DMF                        Basic Orange 14                                                            463                                                                              Nitrophenothiazine                                                                              --           --               0.4                                                                              Methanol                464                                                                              2-Phenadinol      --           --               0.8                                                                              "                       465                                                                              2,8-Diaminodibenzo-                                                                             --           --               0.6                                                                              "                          thiophene                                                                  466                                                                              Cyclo [3,3,3]azine                                                                              Fe(OH).sub.3 sol                                                                      100/30                                                                             --               0.6                                                                              Water/                                                                             10/90                                                                    Methanol                __________________________________________________________________________                         (3)      (4)                                                                  Cl.sup.- conc.                                                                         Time for washing                                                                       Scaling                                                  (1)                                                                              upper: average                                                                         with water after                                                                       Visual evaluation (Amount attached                                            g/m.sup.2)                                               Exp.                                                                             lower: max.-min.                                                                       completion                                                                             Batch No.                                                No.                                                                              ppm      min.     10   30   50  100                                                                              150                                                                              200                __________________________________________________________________________                      413*                                                                             300      60       H(1400)                                                     260-300                                                                    414*                                                                             13       "        H(1200)                                                      8-17                                                                      415*                                                                             280      "        G    H(1000)                                                260-330                                                                    416*                                                                             270      "        C    F    H(900)                                            250-320                                                                    417*                                                                             240      "        C    F    H(850)                                            220-300                                                                    418*                                                                             280      "        G    H(1000)                                                260-320                                                                    419*                                                                             230      "        H(1300)                                                     210-290                                                                    420*                                                                             290      "        G    H(900)                                                 270-350                                                                    421*                                                                             220      "        H(1350)                                                     200-280                                                                    422*                                                                             260      "        G    H(800)                                                 240-310                                                                    423*                                                                             250      "        G    H(800)                                                 230-280                                                                    424*                                                                             300      "        G    H(850)                                                 280-350                                                                    425*                                                                             290      60       C    F    H(700)                                            270-340                                                                    426                                                                              14       15       A    A    A   A  B  C(10)                                   11-18                                                                      427                                                                               9       "        A    A    B   C  D  F(60)                                    6-12                                                                      428                                                                              11       "        A    A    A   A  A  B(1.5)                                   7-13                                                                      429                                                                               8       "        A    A    B   C  D  F(57)                                   6-9                                                                        430                                                                               5       "        A    A    A   B  C  D(19)                                   3-7                                                                        431                                                                              19       "        A    A    A   A  A  B(2.7)                                  17-21                                                                      432                                                                              16       10       A    A    A   B  C  D(18)                                   14-18                                                                      433                                                                              20       "        A    A    B   C  D  F(59)                                   18-23                                                                      434                                                                               8       "        A    A    B   C  D  F(62)                                    5-11                                                                      435                                                                              11       "        A    A    A   A  A  B(1.2)                                    9-14                                                                     436                                                                              14       "        A    A    A   A  B  C(9)                                    11-17                                                                      437                                                                              17       10       A    A    A   B  C  D(18)                                   14-19                                                                      438                                                                              10       10       A    A    B   C  D  F(57)                                    8-12                                                                      439                                                                               6       "        A    A    B   C  D  F(61)                                   5-7                                                                        440                                                                              11       "        A    A    B   C  D  F(60)                                    9-13                                                                      441                                                                              19       "        A    A    A   A  A  B(1.9)                                  16-22                                                                      442                                                                               8       "        A    A    B   C  D  F(58)                                    5-11                                                                      443                                                                              17       "        A    A    A   A  A  B(3)                                    14-20                                                                      444                                                                               9       "        A    A    A   B  C  D(9)                                     5-13                                                                      445                                                                              15       "        A    A    B   C  D  F(59)                                   11-18                                                                      446                                                                              17       "        A    A    B   C  D  F(55)                                   14-20                                                                      447                                                                              11       "        A    A    A   A  A  B(2.5)                                   9-13                                                                      448                                                                              14       "        A    A    B   C  D  F(57)                                   11-17                                                                      449                                                                              12       15       A    B    C   D  E  F(59)                                    9-14                                                                      450                                                                              17       "        A    A    A   A  A  B(1.5)                                  14-20                                                                      451                                                                              18       "        A    A    A   B  C  D(19)                                   14-21                                                                      452                                                                              12       "        A    A    A   A  A  B(1.8)                                  10-14                                                                      453                                                                              20       "        A    A    B   C  D  F(60)                                   18-22                                                                      454                                                                              16       "        A    B    C   D  E  F(65)                                   13-19                                                                      455                                                                               9       "        A    A    B   C  D  F(59)                                    6-12                                                                      456                                                                              11       "        A    A    B   C  D  F(55)                                    8-14                                                                      457                                                                              19       10       A    A    A   A  A  B(1.6)                                  17-21                                                                      458                                                                               8       "        A    A    B   C  D  F(60)                                    5-10                                                                      459                                                                               6       "        A    A    A   A  A  B(1.5)                                  3-7                                                                        460                                                                              11       "        A    B    C   D  E  F(57)                                    9-13                                                                      461                                                                              17       10       A    A    B   C  D  F(56)                                   14-20                                                                      462                                                                              19       "        A    A    A   A  A  B(2.1)                                  15-24                                                                      463                                                                              10       "        A    B    C   D  E  F(60)                                    8-13                                                                      464                                                                               7       "        A    A    B   C  D  F(62)                                   5-9                                                                        465                                                                               6       "        A    B    C   D  E  F(57)                                   5-7                                                                        466                                                                              11       "        A    A    A   A  A  B(1.3)                                   9-13                                                    __________________________________________________________________________     Notes:                                                                        (1) *comparative examples                                                     (2) Conjugated π bond compound concentration in coating solution.          (3) Chloride ion concentration in slurry after completion of                  polymerization                                                                (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h                            

EXAMPLE 7

As shown in Table 7, for each experiment, a conjugated π bond compoundwas dissolved or dispersed in a solvent, optionally with the addition ofan inorganic compound or a polymeric compound as shown in the same Tableto prepare a coating solution. The formulation ratio of the inorganiccompound or the polymeric compound and the concentration of theconjugated π bond compound in the coating solution are also shown inTable 7. The coating solution was applied on the polished inner wallsurface of a stainless steel polymerizer of an inner volume of 1000liters and the portions which may contact with monomers such as stirrer,dried at 60° C. for 20 minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 160 Kg of vinylchloride monomer, 40 Kg of vinyl acetate monomer, 400 Kg of deionizedwater, 600 g of gelatin, 2 Kg of Triclene and 350 g of lauroyl peroxide,and polymerization was carried out at 70° C. for 6 hours. Aftercompletion of polymerization, the polymer was taken out and thepolymerizer was washed internally with water at a flow rate of 0.1 m³/m² hr, as shown in Table 7. The above operations from coating andcharging to washing with water were conducted for each batch and thiswas repeated for a maximum of 200 batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. The conditions and theresults are shown in Table 7.

In Table 7, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 467 and 468 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound.

    TABLE 7      Coating Solution (3)  Solvent Cl.sup.- conc. (4) Time for Scaling (1)     Conjugated π bond compound (a) Inorganic (a)/(b) Polymeric (a)/(c)     (2)  Mix- upper: average washing with Visual evaluation (Amount attached     g/m.sup. 2) Exp. Mixing compound weight compound weight conc.  ing     lower: max.- water after Batch No. No. Kind ratio (b) ratio (c) ratio %     Kind ratio min. ppm completion min. 10 30 50 100 150 200       467* --  --  --   --  350  60 H(1100)                320-390 468* --     --  --   --  10 "  H(1000)            7-12 469* 2,2'-Diaminodiphenyl  --      --  0.5 Methanol  290  " G H(700)           270-350 470* "  Colloidal     100/100 --  1.0 "  270  " C F H(600)    silica       250-320 471* --     Colloidal  0/100 --  1.0 Water  250  " H(900)    silica       230-310     472* 1-Aminophenanthridine  --  Polycyclo- 50/50 1.2 Benzene  280  " C F     H(500)      pentadiene     260-330 473* --  --  Polycyclo-  0/100 1.0 "     250  " H(1000)      pentadiene     230-320 474* 2-Chloroquinizarine  --     --  0.5 Methanol  240       " G H(950)           220-300 475* Pyrazoleanthrone  --  --  0.8     Ethanol  300  " G H(800)           280-350 476* 4,10-Dioxy-1,7-     FeCl.sub.2 100/2  --  0.5 Methanol  310  " C F H(700)  phenanthroline          290-360 477* 1,2-Dihydronaphthalene  Fe(OH).sub.3 sol 100/10  --     0.5 "  240  " C F H(650)           220-280 478* 3,3'-Azopyridine  --  --      0.8 "  260  " G H(850)           240-310 479* 1-Amino-5-phenyl-  --  --      0.8 Ethanol  280  " G H(800)  tetrazole         260-330 480* Phenazine/     70/30 --  --   --    B C F H(500)  Solvent Black 3 481 2,2'-Diaminobiphen     yl  --  --  0.5 Methanol   9 10 A A B C D F(60)            6-11 482 "     Colloidal 100/100 --  1.0 "  10 " A A A A A A(0.5)    silica        8-12     483 Roseindole  Fe(OH).sub.3 sol 100/20  --  0.5 "   8 " A A A A A     B(2.5)            5-10 484 Indophenine  --  --  0.5 "  15 " A A B C D     F(55)           12-17 485 Chlorophyll b  --  --  0.5 Ethanol  20 " A A B     C D F(28)           16-22 486 Phthalocyanine/2,4- 50/50 Orthosilicic     100/50  --  0.7 Methanol  15 " A A A A A A(0.4)  Diaminophenazine  acid          12-17 487 3,3'-Azopyridine  --  --  0.8 "  13 " A A B C D F(56)           10-15 488 7,8-Dioxyflavone  --  --  0.5 Ethanol  14 " A A A B C     D(20)           11-16 489 N--Nitroso-α-naphthyl-  --  --  0.3     Methanol  11 " A A A B C D(18)  hydroxylamine      8-13 490 2-Chloroquinizarine  --  --  0.5 "  10 " A A B C D F(57)          7-12 491 2-(o-Aminophenyl)oxazole  Metatetrasilicic 100/200 --  1.5     Methanol   9 15 A A A A A A(0.7)    acid      6-11 492 2-Phenylazothiazole  --  Poly-  1.0 "  12 " A A A A A B(2.3)        isobutene      9-14 493 1-Amino-5-  --  --  0.8 Ethanol  14 " A A B C     D F(58)  phenyltetrazole         11-16 494 3,2'-Diindolyl  Colloidal     100/20  --  1.0 Methanol  15 " A A A A A A(0.6)    silica       13-17     495 1-Aminophenanthoridine  --  Polycyclo- 50/50 1.5 Benzene  14 " A A A     A A B(3)      pentadiene     11-16 496 4,10-Dioxy-1,7-  FeCl.sub.2 100/2      --  0.5 Methanol  15 " A A A A A A(0.4)  phenanthroline         12-17     497 Phenazine/ 70/30 --  --  0.5 "  17 " A A A A A A(0.7)  Solvent Black     3         14-19 498 Dibenzosuberol  --  --  0.3 "  11 " A A B C D F(56)      8-13 499 α                                               Methoxyph     enazine  --  --  0.7 Ethanol  18 " A A A B C D(21)           16-20 500     2-Phenylbenzothiazole  --  --  0.5 Methanol  14 " A A B C D F(55)        11-16 501 3-Phenylcuomarone  --  --  0.3 Toluene  10 " A A B C D     F(54)            7-12 502 1,2-Dihydronaphthalene  Fe(OH).sub.3 sol     100/10  --  0.5 Methanol   8 10 A A A A A A(0.5)            5-10 503     Perimidine/ 20/80 --  --  0.4 THF  12 " A A A B C D(20)  Phenylrosindorin     e          9-14 504 10-Benzoazo-9-  NiCl.sub.2 100/5  --  0.5 Methanol     9 " A A A A A B(2.1)  phenanthrol          6-11 505 4-Nitroso-1-  --  --      0.7 "  10 " A A A B C D(9)  naphthylamine      7-12 506 Pyrazoleanthrone  --  --  0.8 Ethanol  15 " A A B C D F(60)            12-17     Notes:     (1) *comparative examples     (2) Conjugated π bond compound concentration in coating solution.     (3) Chloride ion concentration in slurry after completion of     polymerization     (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h

EXAMPLE 8

As shown in Table 8, for each experiment, a conjugated π bond compoundwas dissolved or dispersed in a solvent, optionally with the addition ofan inorganic compound or a polymeric compound as shown in the same Tableto prepare a coating solution. The formulation ratio of the inorganiccompound or the polymeric compound and the concentration of theconjugated π bond compound in the coating solution are also shown inTable 8. The coating solution was applied on the polished inner wallsurface of a stainless steel polymerizer of an inner volume of 1000liters and the portions which may contact with monomers such as stirrer,dried at 80° C. for 10 minutes and then thoroughly washed with water.

Next, the thus coated polymerizer was charged with 200 Kg of vinylchloride monomer, 400 Kg of deionized water, 40 g of a partiallysaponified polyvinyl alcohol, 60 g of hydroxypropylmethyl cellulose and80 g of di-2-ethylhexylperoxycarbonate, and polymerization was carriedout at 57° C. for 7 hours. After completion of polymerization, thepolymer was taken out and the polymerizer was washed internally withwater at a flow rate of 0.1 m³ /m² hr, as shown in Table 8. The aboveoperations from coating and charging to washing with water wereconducted for each batch and this was repeated for a maximum of 200batches.

The chloride ion concentration was controlled and the scaling wasevaluated similarly as described in Example 1. Also, the numbers of fisheyes in the products obtained from the polymers produced in the 10th,30th, 50th, 100th, 150th and 200th batches in each experiment weremeasured similarly as in Example 4. The conditions and the results areshown in Table 8.

In Table 8, the Experiment numbers marked with an asterisk (*) indicateComparative examples. In particular, Experiment Nos. 507 and 508 areexamples in which the inner wall surface of the polymerizer wassubjected to no treatment with any compound.

                                      TABLE 8                                     __________________________________________________________________________                      .                                                           Coating Solution                                                              (1)                                                                              Conjugated π bond compound (a)                                                              Inorganic                                                                              (a)/(b)                                                                            Polymeric  (a)/(c)                                                                           (2)                                                                              Solvent                   Exp.           Mixing                                                                             compound weight                                                                             compound   weight                                                                            conc.   Mixing               No.                                                                              Kind        ratio                                                                              (b)      ratio                                                                              (c)        ratio                                                                             %  Kind ratio                __________________________________________________________________________    507*                                                                             --               --            --                --                        508*                                                                             --               --            --                --                        509*                                                                             2-Phenyl-3-      --            --             0.5                                                                              --                           phenylazolindole                                                           510*                                                                             2-Phenyl-3-      Orthosilicic acid                                                                      100/300                                                                            --             1.0                                                                              --                           phenylazolindole                                                           511*                                                                             --               Orthosilicic acid                                                                       0/100                                                                             --             0.8                                                                              --                        512*                                                                             9-Acridine/ 80/20                                                                              Colloidal silica                                                                       100/100                                                                            --             1.5                                                                              --                           Acid Black 2                                                               513*                                                                             2-Phenylthiophene                                                                              --            --             0.5                                                                              --                        514*                                                                             Alizarine        --            --             0.5                                                                              --                        515                                                                              2-Phenyl-3-      --            --             0.5                                                                              Ethanol                      phenylazoindole                                                            516                                                                              2-Phenyl-3-      Orthosilicic acid                                                                      100/300                                                                            --             1.0                                                                              Ethanol                      phenylazoindole                                                            517                                                                              2-Aminophenazine --            --             0.7                                                                              Methanol                  518                                                                              Alizarine        --            --             0.5                                                                              Methanol                  519                                                                              1-Aminophenanthoridine                                                                         Fe(OH).sub.3 sol                                                                       100/10                                                                             --             0.5                                                                              Methanol                  520                                                                              10-Benzoazo-9-   --            --             0.6                                                                              Methanol                     phenanthrol                                                                521                                                                              9-Acrydine/ 80/20                                                                              Collodial silica                                                                       100/100                                                                            --             0.8                                                                              Methanol                     Acid Black 2                                                               522                                                                              Dinitrophenylindazole                                                                          --            --             0.5                                                                              Benzene                   523                                                                              4-Pyridyl-m-     --            --             0.7                                                                              Ethanol                      phenylenediamine                                                           524                                                                              2-Phenylthiophene                                                                              --            Polycyclohexaneoxide                                                                         1.5                                                                              Toluene                   525                                                                              α-Nitroso-β-naphthol                                                                FeCl.sub.2                                                                             100/5                                                                              --             0.7                                                                              Methanol                  __________________________________________________________________________       (3)      (4)                                                                  Cl.sup.- conc.                                                                         Time for washing                                                                       Scaling                                                  (1)                                                                              upper: average                                                                         with water after                                                                       Visual evaluation (Amount attached                                                                  Fish eyes (number)                 Exp.                                                                             lower: max.-min.                                                                       completion                                                                             Batch No.             Batch No.                          No.                                                                              ppm      min.     10   30  50                                                                              100 150                                                                              200 10  30  50                                                                              100 150                                                                              200               __________________________________________________________________________    507*                                                                             290      60       H(1000)               300                                   260-300                                                                    508*                                                                             10       "        H(950)                280                                    8-12                                                                      509*                                                                             280      "        G    H(900)           110 220                               240-300                                                                    510*                                                                             290      "        B    C   F H(950)     20  40  90                                                                              130                         250-310                                                                    511*                                                                             15       "        H(1000)               290                                   13-18                                                                      512*                                                                             270      "        B    C   F H(500)     18  35  80                                                                              100                         230-290                                                                    513*                                                                             250      "        G    H(950)           100 200                               230-280                                                                    514*                                                                             310      "        G    H(900)           90  210                               280-350                                                                    515                                                                              13       10       A    A   A B   C  D(20)                                                                             0   0    2                                                                              9   23 37                   10-15                                                                      516                                                                              12       "        A    A   A A   A  A(0.3)                                                                            0   0    0                                                                              0    2  6                    9-15                                                                      517                                                                              15       "        A    A   A B   C  D(18)                                                                             0   0    6                                                                              11  20 35                   13-18                                                                      518                                                                              17       "        A    A   A B   C  D(21)                                                                             0   0    3                                                                              10  30 41                   15-20                                                                      519                                                                              11       "        A    A   A A   A  A(0.5)                                                                            0   0    0                                                                              0    3  8                    8-14                                                                      520                                                                               9       "        A    A   A B   C  D(20)                                                                             0   0    5                                                                              9   28 42                    7-12                                                                      521                                                                              12       "        A    A   A A   A  A(0.6)                                                                            0   0    0                                                                              0    1  5                   10-14                                                                      522                                                                               7       "        A    A   A B   C  D(20)                                                                             0   0    2                                                                              7   25 40                    5-10                                                                      523                                                                              14       "        A    A   A B   C  D(17)                                                                             0   0    1                                                                              8   20 30                   12-16                                                                      524                                                                              16       "        A    A   A A   B  C(10)                                                                             0   0    0                                                                              2    7 15                   14-19                                                                      525                                                                              12       "        A    A   A A   A  A(0.8)                                                                            0   0    0                                                                              0    4  9                   10-15                                                                      __________________________________________________________________________     (1) *comparative examples                                                     (2) Conjugeted π bond compound concentration in coating solution.          (3) Chloride ion concentration in slurry after completion of                  polymerization                                                                (4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h                            

What is claimed is:
 1. A process for production of a vinyl chloridepolymer comprising polymerizing, by suspension polymerization oremulsion polymerization, vinyl chloride monomer or a mixture of vinylchloride monomer with a vinyl monomer copolymerizable with said vinylchloride monomer in an aqueous medium in a polymerizer, wherein theinner wall surface of the polymerizer and portions of the auxiliaryequipment thereof which come into contact with the monomer duringpolymerization have been previously coated with a scaling preventivecoating comprising at least one component selected from dyes andpigments, and the chloride ion concentration in the reaction mixture iscontrolled to not higher than 100 ppm during the polymerization.
 2. Aprocess according to claim 1, wherein said scaling preventive coatingcomprises at least one component selected from azo dyes and pigments,anthraquinone dyes and pigments, indigoid dyes and pigments,phthalocyanine dyes and pigments, carbonium dyes and pigments,quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes,benzoquinone and naphthoquinone dyes, naphthalimide dyes and pigments,perinone dyes, sulfide dyes, fluorescent dyes, and azoic dyes.
 3. Aprocess according to claim 2, wherein said scaling preventive coatingcomprises an azine dye.
 4. A process according to claim 1, wherein saidscaling preventive coating further comprises an inorganic compound.
 5. Aprocess according to claim 4, wherein said inorganic compound isselected from silicic acids; silicates; salts of magnesium, calcium,barium, zinc, aluminum, tin, iron, nickel, cobalt, chromium, molybdenum,manganese, copper, silver and platinum; and inorganic colloids.
 6. Aprocess according to claim 5, wherein said inorganic compound is asilicate, silicic acid colloid or ferric hydroxide colloid.
 7. A processaccording to claim 4, wherein said scaling preventive coating comprisesat least one component selected from azo dyes and pigments,anthraquinone dyes and pigments, indigoid dyes and pigments,phthalocyanine dyes and pigments, carbonium dyes and pigments,quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes,benzoquinone and naphthoquinone dyes, naphthalimide dyes and pigments,perinone dyes, sulfide dyes, fluorescent dyes, and azoic dyes.
 8. Aprocess according to claim 7, wherein said scaling preventive coatingcomprises an azine dye.
 9. A process according to claim 1, wherein afixing agent is used for enchancement of the fixing characteristic ofsaid scaling preventive coating.
 10. A process according to claim 9,wherein said fixing agent is at least one selected from olefin polymers,diene polymers, acetylene polymers, aliphatic vinyl or vinylidenepolymers, aromatic vinyl polymers, heterocyclic vinyl polymers, acrylicor methacrylic polymers, polyethers, polysulfides, polysulfones,poly(alkylene diisocyanate), poly(5-iminohydantoin),poly(perfluoroglutaronitrile), poly(1-perfluorobutyrylaziridine),polyesters, polyamides, polyureas, polyurethanes, linear condensedpoplymers, heterocyclic condensed polymers, natural polymers, modifiednatural polymers, polysiloxanes, organic metal polymers and inorganicpolymers.
 11. A process according to claim 1, wherein portions of arecovery system for unreacted monomers where scales may stick arepreviously coated with the scaling preventive coating.
 12. A processaccording to claim 1, wherein the inner wall surface of the polymerizerand the portions of the auxiliary equipment contacting the monomer havea surface roughness of 10 μm or less.